WO2000043474A2 - Compositions de lavage de la vaisselle comprenant un alkylbenzene modifie - Google Patents

Compositions de lavage de la vaisselle comprenant un alkylbenzene modifie Download PDF

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Publication number
WO2000043474A2
WO2000043474A2 PCT/US1999/029838 US9929838W WO0043474A2 WO 2000043474 A2 WO2000043474 A2 WO 2000043474A2 US 9929838 W US9929838 W US 9929838W WO 0043474 A2 WO0043474 A2 WO 0043474A2
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alkyl
mixture
branched
mixtures
hand dishwashing
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PCT/US1999/029838
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English (en)
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WO2000043474A3 (fr
Inventor
Kevin Lee Kott
Jeffrey John Scheibel
Roland George Severson
Thomas Anthony Cripe
James C. T. R. Burckett-St. Laurent
William Michael Scheper
Chandrika Kasturi
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The Procter & Gamble Company
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Priority to JP2000594883A priority Critical patent/JP2002535439A/ja
Priority to EP99965276A priority patent/EP1144568A3/fr
Priority to BR9916936-3A priority patent/BR9916936A/pt
Publication of WO2000043474A2 publication Critical patent/WO2000043474A2/fr
Publication of WO2000043474A3 publication Critical patent/WO2000043474A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to dishwashing compositions comprising particular types of inproved alkylbenzene sulfonate surfactant mixtures adapted for use by controlling compositional parameters, especially a 2/3-phenyl index and a 2-methyl-2- phenyl index.
  • compositions containing both branched and linear alkylbenzene sulfonate surfactants are complex.
  • such compositions can be highly varied, containing one or more different kinds of branching in any of a number of positions on the aliphatic chain.
  • a very large number, e.g., hundreds, of distinct chemical species are possible in such mixtures. Accordingly there is an onerous burden of experimentation if it is desired to improve such compositions so that they can clean better in detergent compositions while at the same time remaining biodegradable.
  • the formulator's knowledge is key to guiding this effort.
  • modified alkylbenzene sulfonate surfactant mixtures leads to improved cleaning of tough food stains, removal of grease/oil, improved benefits in dissolution, rinsing and low temperature product stability when compared to the use LAS in conventional detergent compositions.
  • composition of a modified alkylbenzene sulfonate surfactant mixture comprising:
  • L is an acyclic aliphatic moiety consisting of carbon and hydrogen, said L having two methyl termini and said L having no substituents other than A, R and R ; and wherein said mixture of branched alkylbenzene sulfonates contains two or more, preferably at least three, optionally more, of said branched alkylbenzene sulfonates differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulfonates has
  • R , L and R a sum of carbon atoms in R , L and R of from 9 to 15, preferably from 10 to 14;
  • M is a cation or cation mixture, preferably M is selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably M is selected from H, Na, K and mixtures thereof, more preferably still, M is selected from H, Na, and mixtures thereof, M having a valence q, typically from 1 to 2, preferably 1; a and b are integers selected such that said branched alkylbenzene sulfonates are electroneutral (a is typically from 1 to 2, preferably 1, b is 1); R 1 is C ⁇ -C alkyl, preferably C ⁇ -C 2 alkyl, more preferably methyl; R 2 is selected from H and C ⁇ -C 3 alkyl (preferably H and C ⁇ -C alkyl (preferably H and C ⁇ -C al
  • Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein said Y has a sum of carbon atoms of from 9 to 15, preferably from 10 to 14, and said Y has an average aliphatic carbon content of from about 10.0 to about 14.0, preferably from about 11.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms; and wherein said modified alkylbenzene sulfonate surfactant mixture is further characterized by a 2/3-phenyl index of from about 160 to about 275, preferably from about 170 to about 265, more preferably from about 180 to about 255; and also preferably wherein said modified alkylbenzene sulfonate surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, more preferably still, from
  • a modified alkylbenzene sulfonate surfactant mixture preferably from about 0.01% to about 95%o, more preferably from about 1%> to about 50%>, even more preferably from about 2%> to about 30%>, by weight of composition, comprising the product of a process comprising the steps of:
  • composition of a conventional hand dishwashing adjunct from about 0.00001%) to about 99.9%> by weight of composition of a conventional hand dishwashing adjunct; wherein said composition is further characterized by a 2/3-phenyl index of from about 275 to about 10,000.
  • a modified alkylbenzene sulfonate surfactant mixture preferably from about 0.01%) to about 95%o, more preferably from about 1%> to about 50%), even more preferably from about 2%o to about 30%>, by weight of composition, consisting essentially of the product of a process comprising the steps, in sequence, of:
  • A is an acyclic alpha-olefmic moiety consisting of carbon and hydrogen and containing one terminal methyl and one terminal olefmic methylene;
  • B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two terminal methyls and one internal olefmic methylene;
  • R QR wherein Q is an acyclic aliphatic primary terminal alcohol moiety consisting of carbon, hydrogen and oxygen and containing one terminal methyl;
  • C 2 o (preferably C 9 -C ⁇ 5 , more preferably Cio-C ⁇ ) linear alkylating agent selected from C 9 -C 2 o (preferably C 9 -C ⁇ 5 , more preferably C ⁇ n-C 1 ) linear aliphatic olefins, C 9 -C o (preferably C 9 - 5 , more preferably C ⁇ o-C 14 ) linear aliphatic alcohols and mixtures thereof; wherein said alkylating mixture contains said branched alkylating agents having at least two different carbon numbers in said C 9 -C 2 o (preferably C 9 - 5 , more preferably C ⁇ o-C 14 ) range, and has a mean carbon content of from about 9.0 to about 15.0 carbon atoms, preferably from about 10.0 to about 14.0, more preferably from about 11.0 to about 13.0, more preferably still from about 11.5 to about 12.5; and wherein said components (a) and (b) are at a weight ratio of at least about 15:85 (preferably
  • the invention is not intended to encompass any wholly conventional hand dishwashing compositions, such as those based exclusively on linear alkylbenzene sulfonates made by any process, or exclusively on known unacceptably branched alkylbenzene sulfonates such as ABS or TPBS.
  • the detergent compositions of the present invention comprise any alkylbenzene sulfonate surfactant other than said modified alkylbenzene sulfonate surfactant mixture (for example as a result of blending into the detergent composition one or more commercial, especially linear, typically linear C l ⁇ -C 14 , alkylbenzene sulfonate surfactants), said composition is further characterized by an overall 2/3-phenyl index of at least about 200, preferably at least about 250, more preferably at least about 350, more preferably still, at least about 500, wherein said overall 2/3-phenyl index is determined by measuring 2/3-phenyl index, as defined herein, on a blend of said modified alkylbenzene sulfonate surfactant mixture and said any other alkylbenzene sulfonate to be added to said composition, said blend, for purposes of measurement, being prepared from aliquots of said modified alkylbenzene sulfonate surfactant mixture
  • the modified alkylbenzene sulfonate surfactant mixture in the hand dishwashing composition accoring to the composition according to the first embodiment is prepared by a process comprising a step selected from: blending a mixture of branched and linear alkylbenzene sulfonate surfactants having a 2/3-phenyl index of 500 to 700 with an alkylbenzene sulfonate surfactant mixture having a 2/3-phenyl index of 75 to 160 (typically this alkylbenzene sulfonate surfactant is a commercial C ⁇ o-C ⁇ 4 linear alkylbenzene sulfonate surfactant, e.g., DETAL ® process LAS or HF process LAS though in general any commercial linear (LAS) or branched (ABS, TPBS) type can be used); and blending a mixture of branched and linear alkylbenzenes having a 2/3-phenyl index of 500 to 700 with an alkylbenzen
  • the invention encompasses the addition of useful hydrotrope precursors and/or hydrotropes, such as C ⁇ -C 8 alkylbenzenes, more typically toluenes, cumenes, xylenes, naphthalenes, or the sulfonated derivatives of any such materials, minor amounts of any other materials, such as tribranched alkylbenzene sulfonate surfactants, dialkylbenzenes and their derivatives, dialkyl tetralins, wetting agents, processing aids, and the like.
  • useful hydrotrope precursors and/or hydrotropes such as C ⁇ -C 8 alkylbenzenes, more typically toluenes, cumenes, xylenes, naphthalenes, or the sulfonated derivatives of any such materials, minor amounts of any other materials, such as tribranched alkylbenzene sulfonate surfactants, dialkylbenzenes and their derivatives
  • compositions of their use such as a method contacting soiled tableware in need of cleaning with either a neat or an aqueous solution of the composition of the invention.
  • Such methods may optionally include the step of diluting the composition with water.
  • the composition may be applied, either neat or as an aqueous solution, directly to the tableware or surface to be cleaned or directly to a cleaning implement, such as a sponge or a wash cloth.
  • a cleaning implement such as a sponge or a wash cloth.
  • Such a modified alkylbenzene sulfonate surfactant mixture can be made as the product of a process using as catalyst a zeolite selected from mordenite, offretite and H-ZSM-12 in at least partially acidic form, preferably an acidic mordenite (in general certain forms of zeolite beta can be used as an alternative but are not preferred).
  • zeolite selected from mordenite, offretite and H-ZSM-12 in at least partially acidic form, preferably an acidic mordenite (in general certain forms of zeolite beta can be used as an alternative but are not preferred).
  • Another preferred modified alkylbenzene sulfonate surfactant mixture consists essentially of said mixture of branched alkylbenzene sulfonates and nonbranched alkylbenzene sulfonates, wherein said 2- methyl-2 -phenyl index of said modified alkylbenzene sulfonate surfactant mixture is less than about 0.1, and wherein in said mixture of branched and nonbranched alkylbenzene sulfonates, said average aliphatic carbon content is from about 11.5 to about 12.5 carbon atoms; said R 1 is methyl; said R 2 is selected from H and methyl provided that in at least about 0.7 mole fraction of said branched alkylbenzene sulfonates R 2 is H; and wherein said sum of carbon atoms in R 1 , L and R 2 is from 10 to 14; and further wherein in said mixture of nonbranched alkylbenzene sulfonates, said
  • methyl termini and/or “terminal methyl” mean the carbon atoms which are the terminal carbon atoms in alkyl moieties, that is L, and or Y of formula (I) and formula (II) respectively are always bonded to three hydrogen atoms. That is, they will form a CH 3 - group. To better explain this, the structure below shows the two terminal methyl groups in an alkylbenzene sulfonate.
  • ABS alkylbenzene
  • LAB linear alkylbenzene
  • MLAS modified alkylbenzene sulfonate mixtures of the invention.
  • the surfactant mixtures herein are preferably substantially free from impurities selected from tribranched impurities, dialkyl tetralin impurities and mixtures thereof.
  • substantially free it is meant that the amounts of such impurities are insufficient to contribute positively or negatively to the cleaning effectiveness of the composition.
  • Structures (w) and (x) nonlimitingly illustrate less preferred compounds of Formula (I) which can be present, at lower levels than the above-illustrated preferred types of stuctures, in the modified alkylbenzene sulfonate surfactant mixtures of the invention and the resulting detergent compositions.
  • Structures (y), (z), and (aa) nonlimitingly illustrate compounds broadly within Formula (I) that are not preferred but which can be present in the modified alkylbenzene sulfonate surfactant mixtures of the invention and the resulting detergent compositions.
  • Structure (bb) is illustrative of a tri-branched structure not within Formula (I), but that can be present as an impurity.
  • the branched alkylbenzene sulfonate is the product of sulfonating a branched alkylbenzene, wherein the branched alkylbenzene is produced by alkylating benzene with a branched olefin over an zeolite beta catalyst which may be fluoridated or non- fluoridated, more preferably the zeolite beta catalyst is an acidic zeolite beta catalyst.
  • the preferred acidic zeolite beta catalysts are HF-treated calcined zeolite beta catalysts.
  • modified alkylbenzene sulfonate surfactant mixtures herein can be made by the steps of:
  • step (I) is a modified alkylbenzene mixture in accordance with the invention.
  • product of step (II) is a modified alkylbenzene sulfonic acid mixture in accordance with the invention.
  • neutralization step (HI) is conducted as generally taught herein, the product of step (III) is a modified alkylbenzene sulfonate surfactant mixture in accordance with the invention.
  • step (D-) the alkylation is performed at a temperature of from about 125°C to about 230°C, preferably from about 175°C to about 215°C and at a pressure of from about 50 psig to about 1000 psig, preferably from about 100 psig to about 250 psig.
  • Time for this alkylation reaction can vary, however it is further preferred that the time for this alkylation be from about 0.01 hour to about 18 hours, more preferably, as rapidly as possible, more typically from about 0.1 hour to about 5 hours, or from about 0.1 hour to about 3 hours.
  • step (I) it is found preferable in step (I) to couple together the use of relatively low temperatures (e.g., 175°C to about 215°C) with reaction times of medium duration (1 hour to about 8 hours) in the above-indicated ranges.
  • relatively low temperatures e.g., 175°C to about 215°C
  • reaction times of medium duration e.g., 1 hour to about 8 hours
  • the alkylation "step" (I) herein can be "staged” so that two or more reactors operating under different conditions in the defined ranges may be useful. By operating a plurality of such reactors, it is possible to allow for material with less preferred 2-methyl-2-phenyl index to be initially formed and, surprisingly, to convert such material into material with a more preferred 2-methyl-2- phenyl index.
  • a surprising discovery as part of the present invention is that one can attain low levels of quaternary alkylbenzenes in zeolite beta catalyzed reactions of benzene with branched olefins, as characterized by a 2-methyl-2-phenyl index of less than 0.1.
  • the present invention uses a particularly defined alkylation catalyst.
  • Such catalyst comprises a moderate acidity, medium-pore zeolite defined in detail hereinafter.
  • a particularly preferred alkylation catalyst comprises at least partially dealuminized acidic nonfluoridated or at least partially dealuminized acidic fluoridated zeolite beta.
  • alkylation catalysts are readily determined to be unsuitable. Unsuitable alkylation catalysts include the DETAL® process catalysts, aluminum chloride, HF, and many others. Indeed no alkylation catalyst currently used for alkylation in the commercial production of detergent linear alkylbenzenesulfonates is suitable.
  • suitable alkylation catalyst herein is selected from shape-selective moderately acidic alkylation catalysts, preferably zeolitic. More particularly, the zeolite in such catalysts for the alkylation step step I is preferably selected from the group consisting of ZSM-4, ZSM-20, and zeolite beta, more preferably zeolite beta, in at least partially acidic form.
  • the zeolite in step I is substantially in acid form and is contained in a catalyst pellet comprising a conventional binder and further wherein said catalyst pellet comprises at least about 1 %, more preferably at least 5%, more typically from 50% to about 90%, of said zeolite, wherein said zeolite is preferably a zeolite beta.
  • suitable alkylation catalyst is typically at least partially crystalline, more preferably substantially crystalline not including binders or other materials used to form catalyst pellets, aggregates or composites.
  • the catalyst is typically at least partially acidic zeolite beta. This catalyst is useful for the alkylation step identified as step I in the claims hereinafter.
  • the largest pore diameter characterizing the zeolites useful in the present alkylation process may be in the range of 6Angstrom to 8Angstrom, such as in zeolite beta. It should be understood that, in any case, the zeolites used as catalysts in the alkylation step of the present process have a major pore dimension intermediate between that of the large pore zeolites, such as the X and Y zeolites, and the relatively smaller pore size zeolites such as mordenite, offretite, HZSM-12 and HZSM-5. Indeed ZSM-5 has been tried and found inoperable in the present invention.
  • the pore size dimensions and crystal structures of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES by W. M. Meier and D. H. Olson, published by the Structure Commission of the International Zeolite Association (1978 and more recent editions) and distributed by Polycrystal Book Service, Pittsburgh, Pa.
  • the zeolites useful in the alkylation step of the instant process generally have at least 10 percent of the cationic sites thereof occupied by ions other than alkali or alkaline-earth metals.
  • Typical but non-limiting replacing ions include ammonium, hydrogen, rare earth, zinc, copper and aluminum. Of this group, particular preference is accorded ammonium, hydrogen, rare earth or combinations thereof.
  • the zeolites are converted to the predominantly hydrogen form, generally by replacement of the alkali metal or other ion originally present with hydrogen ion precursors, e.g., ammonium ions, which upon calcination yield the hydrogen form.
  • This exchange is conveniently carried out by contact of the zeolite with an ammonium salt solution, e.g., ammonium chloride, utilizing well known ion exchange techniques.
  • an ammonium salt solution e.g., ammonium chloride
  • the extent of replacement is such as to produce a zeolite material in which at least 50 percent of the cationic sites are occupied by hydrogen ions.
  • the zeolites may be subjected to various chemical treatments, including alumina extraction (dealumination) and combination with one or more metal components, particularly the metals of Groups ILB, HI, IV, VI, VII and VEL It is also contemplated that the zeolites may, in some instances, desirably be subjected to thermal treatment, including steaming or calcination in air, hydrogen or an inert gas, e.g. nitrogen or helium.
  • thermal treatment including steaming or calcination in air, hydrogen or an inert gas, e.g. nitrogen or helium.
  • a suitable modifying treatment entails steaming of the zeolite by contact with an atmosphere containing from about 5 to about 100%> steam at a temperature of from about 250°C to 1000°C. Steaming may last for a period of between about 0.25 and about 100 hours and may be conducted at pressures ranging from sub-atmospheric to several hundred atmospheres.
  • intermediate pore size crystalline zeolites in another material, e.g., a binder or matrix resistant to the temperature and other conditions employed in the process.
  • matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica, and or metal oxides.
  • Matrix materials can be in the form of gels including mixtures of silica and metal oxides. The latter may be either naturally occurring or in the form of gels or gelatinous precipitates.
  • Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite.
  • Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • the intermediate pore size zeolites employed herein may be compounded with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica- titania, as well as ternary combinations, such as silica-alumina-thoria, silica-alumina- zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the matrix may be in the form of a cogel.
  • the relative proportions of finely divided zeolite and inorganic oxide gel matrix may vary widely, with the zeolite content ranging from between about 1 to about 99% by weight and more usually in the range of about 5 to about 80%> by weight of the composite.
  • a group of zeolites which includes some useful for the alkylation step herein have a silica: alumina ratio of at least 10:1, preferably at least 20:1.
  • the silica: alumina ratios referred to in this specification are the structural or framework ratios, that is, the ratio for the SiO 4 to the AlO 4 tetrahedra. This ratio may vary from the silica: alumina ratio determined by various physical and chemical methods. For example, a gross chemical analysis may include aluminum which is present in the form of cations associated with the acidic sites on the zeolite, thereby giving a low silica:alumina ratio.
  • thermogravimetric analysis TGA
  • a low ammonia titration may be obtained if cationic aluminum prevents exchange of the ammonium ions onto the acidic sites.
  • the zeolites When the zeolites have been prepared in the presence of organic cations they are catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540°C. for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 540°C in air. The presence of organic cations in the forming solution may not be absolutely essential to the formation of the zeolite; but it does appear to favor the formation of this special type of zeolite. Some natural zeolites may sometimes be converted to zeolites of the desired type by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination.
  • the zeolites preferably have a crystal framework density, in the dry hydrogen form, not substantially below about 1.6 g.cm -3.
  • the dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite Structure by W. M. Meier included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London, 1968. Reference is made to this paper for a discussion of the crystal framework density. A further discussion of crystal framework density, together with values for some typical zeolites, is given in U.S. Pat. No. 4,016,218, to which reference is made.
  • the zeolite When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. It has been found that although the hydrogen form of the zeolite catalyzes the reaction successfully, the zeolite may also be partly in the alkali metal form.
  • Prefered zeolite catalysts include zeolite beta, HZSM-4, HZSM-20 and HZSM- 38. Most prefered catalyst is acidic zeolite beta.
  • a zeolite beta suitable for use herein is disclosed in US3,308,069 to which reference is made for details of this zeolite and its preparation.
  • Zeolite beta catalysts in the acid form are also commercially available as Zeocat PB/H from Zeochem.
  • Other zeolite beta catalysts suitable for use can be provided by UOP Chemical Catalysts and Zeolyst International.
  • alkylation catalysts may be used herein provided that the alkylation catalyst 1) can accommodate into the smallest pore diameter of said catalyst said branched olefins described herein and 2) selectively alkylate benzene with said branched olefins and/or mixture with nonbranched olefins with sufficient selectivity to provide the 2/3 -Ph index values defined herein.
  • a hydrotrope or hydrotrope precursor is added either after step (I), during or after step (II) and prior to step (HI) or during or after step (HI).
  • the hydrotropes are selected from any suitable hydrotrope, typically a sulfonic acid or sodium sulfonate salt of toluene, cumene, xylene, napthalene or mixtures thereof.
  • the hydrotropes precursors are selected from any suitable, hydrotrope precursor typically toluene, cumene, xylene, napthalene or mixtures thereof. Sulfonation and Workup or Neutralization (Steps II / HI)
  • the sulfonating step (H) is performed using a sulfonating agent, preferably selected from the group consisting of sulfuric acid, sulfur trioxide with or without air, chlorosulfonic acid, oleum, and mixtures thereof. Furthermore, it is preferable in step (H) to remove components other than monoalkylbenzene prior to contacting the product of step (I) with sulfonating agent.
  • a sulfonating agent preferably selected from the group consisting of sulfuric acid, sulfur trioxide with or without air, chlorosulfonic acid, oleum, and mixtures thereof.
  • sulfonation of the modified alkylbenzenes in the instant process can be accomplished using any of the well-known sulfonation systems, including those described in “Detergent Manufacture Including Zeolite Builders and other New Materials", Ed. Sittig., Noyes Data Corp., 1979, as well as in Vol. 56 in “Surfactant Science” series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled “Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108 which includes 297 literature references.
  • any convenient workup steps may be used in the present process.
  • Common practice is to neutralize after sulfonation with any suitable alkali.
  • the neutralization step can be conducted using alkali selected from sodium, potassium, ammonium, magnesium and substituted ammonium alkalis and mixtures thereof.
  • Potassium can assist solubility
  • magnesium can promote soft water performance and substituted ammonium can be helpful for formulating specialty variations of the instant surfactants.
  • the invention encompasses any of these derivative forms of the modified alkylbenzenesulfonate surfactants as produced by the present process and their use in consumer product compositions.
  • acid form of the present surfactants can be added directly to acidic cleaning products, or can be mixed with cleaning ingredients and then neutralized.
  • the neutralisation step (DI) is performed using a basic salt.
  • the basic salt having a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, substituted ammonium, and mixtures thereof and an anion selected from hydroxide, oxide, carbonate, silicate, phosphate and mixtures thereof. More preferably the basic salt is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, and mixtures thereof.
  • the processes are tolerant of variation, for example conventional steps can be added before, in parallel with, or after the outlined steps (I), (II) and (HI). This is especially the case for accomodating the use of hydrotropes or their precursors.
  • EXAMPLE 1 Mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol, 6-methyl-6-undecanol and 6-methyl-6-dodecanol (A starting-material for branched olefins) A mixture of 4.65 g of 2-pentanone, 20.7 g of 2-hexanone, 51.0 g of 2-heptanone, 36.7 g of 2-octanone and 72.6 g of diethyl ether is added to an addition funnel.
  • the ketone mixture is then added dropwise over a period of 2.25 hours to a nitrogen blanketed stirred three neck 2 L round bottom flask, fitted with a reflux condenser and containing 600 mL of 2.0 M n-pentylmagnesium bromide in diethyl ether and an additional 400 mL of diethyl ether. After the addition is complete the reaction mixture is stirred an additional 2.5 hours at 20°C. The reaction mixture is then added to 1kg of cracked ice with stirring. To this mixture is added 393.3 g of 30%) sulphuric acid solution. The aqueous acid layer is drained and the remaining ether layer is washed twice with 750 mL of water. The ether layer is then evaporated under vacuum to yield 176.1 g of a mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol, 6-methyl-6-undecanol and 6-methyl-6- dodecanol.
  • EXAMPLE 2 Substantially Mono Methyl Branched Olefin Mixture With Randomized Branching an alkylating agent for preparing modified alkylbenzenes in accordance with the invention a) A 174.9 g sample of the mono methyl branched alcohol mixture of example 1 is added to a nitrogen blanketed stirred three neck round bottom 500 mL flask, fitted with a Dean Stark trap and a reflux condenser along with 35.8 g of a shape selective zeolite catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H). With mixing, the mixture is then heated to about 110-155°C and water and some olefin is collected over a period of 4-5 hours in the Dean Stark trap.
  • a shape selective zeolite catalyst acidic mordenite catalyst ZeocatTM FM-8/25H
  • Residual olefin and catalyst in the container are washed into the autoclave with 300 mL of n-hexane and the autoclave is sealed.
  • 2000 g of benzene (contained in a isolated vessel and added by way of an isolated pumping system inside the isolated autoclave cell) is added to the autoclave.
  • the autoclave is purged twice with 250 psig N2, and then charged to 60 psig N2.
  • the mixture is stirred and heated to about 200°C for about 4-6 hours.
  • the autoclave is cooled to about 20°C overnight.
  • the valve is opened leading from the autoclave to the benzene condenser and collection tank.
  • the autoclave is heated to about 120°C with continuous collection of benzene. No more benzene is collected by the time the reactor reaches 120°C.
  • the reactor is then cooled to 40°C and 750 g of n-hexane is pumped into the autoclave with mixing.
  • the autoclave is then drained to remove the reaction mixture.
  • the reaction mixture is filtered to remove catalyst and the n-hexane is evaporated under low vacuum.
  • the product is then distilled under high vacuum (1-5 mm of Hg).
  • the substantially mono methyl branched alkylbenzene mixture with a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.005 is collected from 76°C - 130°C (167 g).
  • EXAMPLE 4 Substantially Mono Methyl Branched Alkylbenzenesulfonic Acid Mixture With a 2/3-Phenyl Index of about 200 and a 2-Methyl-2-Phenyl Index of About 0.005
  • the product of example 3 is sulfonated with a molar equivalent of chlorosulfonic acid using methylene chloride as solvent.
  • the methylene chloride is removed to give 210 g of a substantially mono methyl branched alkylbenzenesulfonic acid mixture with a 2/3- Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.005.
  • EXAMPLE 6 Substantially Linear Alkylbenzene Mixture With a 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of about 0.02.
  • An alkylbenzene mixture used as a component of modified alkylbenzenes A mixture of chain lengths of substantially linear alkylbenzenes with a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.02 is prepared using a shape zeolite catalyst (acidic beta zeolite catalyst Zeocat PB/H).
  • Neodene A mixture of 15.1 g of Neodene (R)10, 136.6 g of Neodene(R)l 112, 89.5 g of Neodene(R)12 and 109.1 g of 1- tridecene is added to a 2 gallon stainless steel, stirred autoclave along with 70 g of a shape selective catalyst (acidic beta zeolite catalyst Zeocat M PB/H).
  • Neodene is a trade name for olefins from Shell Chemical Company. Residual olefin and catalyst in the container are washed into the autoclave with 200 mL of n-hexane and the autoclave is sealed.
  • benzene (contained in a isolated vessel and added by way of an isolated pumping system inside the isolated autoclave cell) is added to the autoclave.
  • the autoclave is purged twice with 250 psig N2, and then charged to 60 psig N2.
  • the mixture is stirred and heated to 170°C to 175°C for about 18 hours then cooled to 70-80°C.
  • the valve is opened leading from the autoclave to the benzene condenser and collection tank.
  • the autoclave is heated to about 120°C with continuous collection of benzene in collection tank. No more benzene is collected by the time the reactor reaches 120°C.
  • the reactor is then cooled to 40°C and 1 kg of n-hexane is pumped into the autoclave with mixing.
  • the autoclave is then drained to remove the reaction mixture.
  • the reaction mixture is filtered to remove catalyst and the n-hexane is evaporated under low vacuum.
  • the product is then distilled under high vacuum (1-5 mm of Hg).
  • the substantially linear alkylbenzene mixture with a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.02 is collected from 85°C - 150°C (426.2 g).
  • EXAMPLE 7 Substantially Linear Alkylbenzenesulfonic Acid Mixture With a 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of about 0.02 (An alkylbenzenesulfonic acid mixture to be used as a component of modified alkylbenzenesulfonic acid in accordance with the invention) 422.45 g of the product of example 6 is sulfonated with a molar equivalent of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride is removed to give 574 g of a substantially linear alkylbenzenesulfonic acid mixture with a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.02.
  • EXAMPLE 8 Substantially Linear Alkylbenzene Sulfonic Acid Mixture With a 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of About 0.02
  • the substantially linear alkylbenzene sulfonic acid mixture of example 7 is neutralized with a molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 613 g of the substantially linear alkylbenzene sulfonate, sodium salt mixture with a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.02.
  • EXAMPLE 9 10-Dimethyl-2-undecanol (A starting-material for branched olefins)
  • a glass autoclave liner is added 299 g of geranylacetone, 3.8 g or 5% ruthenium on carbon and 150 ml of methanol.
  • the glass liner is sealed inside a 3 L, stainless steel, rocking autoclave and the autoclave purged once with 250 psig N 2 , once with 250 psig H 2 and then charged with 1000 psig H 2 .
  • the reaction mixture is heated. At about 75°C, the reaction initiates and begins consuming H 2 and exotherms to 170-180°C.
  • the temperature has dropped to 100-110°C and the pressure dropped to 500 psig.
  • the autoclave is boosted to 1000 psig with H 2 and mixed at 100-110°C for an additional 1 hour and 40 minutes with the reaction consuming an additional 160 psig H 2 but at which time no more H consumption is observed.
  • the reaction mixture removed, filtered to remove catalyst and concentrated by evaporation of methanol under vacuum to yield 297.75 g of 6,10-dimethyl-2-undecanol.
  • EXAMPLE 10 5 ,7-Dimethyl-2-decanol (A starting-material for branched olefins) To a glass autoclave liner is added 249 g of 5,7-dimethyl-3,5,9-decatrien-2-one, 2.2 g or 5% ruthenium on carbon and 200 ml of methanol. The glass liner is sealed inside a 3 L, stainless steel, rocking autoclave and the autoclave purged once with 250 psig N 2 , once with 250 psig H 2 and then charged with 500 psig H 2 . With mixing, the reaction mixture is heated. At about 75°C, the reaction initiates and begins consuming H 2 and exotherms to 170°C.
  • EXAMPLE 11 4,8-Dimethyl-2-nonanol (A starting-material for branched olefins)
  • a mixture of 671.2 g of citral and 185.6 g of diethyl ether is added to an addition funnel.
  • the citral mixture is then added dropwise over a five hour period to a nitrogen blanketed, stirred, 5 L, 3-neck, round bottom flask equipped with a reflux condenser containing 1.6 L of 3.0 M methylmagnesium bromide solution and an additional 740 ml of diethyl ether.
  • the reaction flask is situated in an ice water bath to control exotherm and subsequent ether reflux.
  • EXAMPLE 12 Substantially Dimethyl Branched Olefin Mixture With Randomized Branching (A branched olefin mixture which is an alkylating agent for preparing modified alkylbenzenes in accordance with the invention)
  • a branched olefin mixture which is an alkylating agent for preparing modified alkylbenzenes in accordance with the invention
  • To a nitrogen blanketed, 2 L, 3-neck round bottom flask equipped with thermometer, mechanical stirrer and a Dean-Stark trap with reflux condenser is added 225 g of 4,8- dimethyl-2-nonanol (example 11), 450 g of 5,7-dimethyl-2-decanol (example 10), 225 g of 6,10-dimethyl-2-undecanol (example 9) and 180 g of a shape selective zeolite catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H).
  • the mixture With mixing, the mixture is heated (135-160°C) to the point water and some olefin is driven off and collected in Dean-Stark trap at a moderate rate. After a few hours, the rate of water collection slows and the temperature rises to 180-195°C where the reaction is allowed to mix for an additional 2-4 hours.
  • the dimethyl branched olefin mixture remaining in the flask is filtered to remove the catalyst.
  • the catalyst filter cake is slurried with 500 ml of hexane and vacuum filtered. The catalyst filter cake is washed twice with 100 ml of hexane and the filtrate concentrated by evaporation of the hexane under vacuum. The resulting product is combined with the first filtrate to give 820 g of dimethyl branched olefin mixture with randomized branching.
  • EXAMPLE 13 Substantially Dimethyl Branched Alkylbenzene Mixture With Randomized Branching and 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of About 0.04
  • 820 g of the dimethyl branched olefin mixture of example 12 and 160 g of a shape selective zeolite catalyst acidic beta zeolite catalyst Zeocat PB/H
  • the autoclave is purged twice with 80 psig N2 and then charged to 60 psig N2.
  • benzene obtained in a isolated vessel and added by way of an isolated pumping system inside the isolated autoclave cell
  • the mixture is stirred and heated to about 205°C for about 8 hours.
  • the autoclave is cooled to about 30°C overnight.
  • the valve is opened leading from the autoclave to the benzene condenser and collection tank.
  • the autoclave is heated to about 120°C with continuous collection of benzene. No more benzene is collected by the time the reactor reaches 120°C and the reactor is then cooled to 40°C.
  • the autoclave is then drained to remove the reaction mixture.
  • the reaction mixture is filtered to remove catalyst and vacuum pulled on the mixture to remove any residual traces of benzene.
  • the product is distilled under vacuum (1-5 mm of Hg).
  • the dimethyl branched alkylbenzene mixture with randomized branching and 2/3-Phenyl Index of about 200 and a 2-methyl -2 -phenyl index of about 0.04 is collected from 88°C - 160°C.
  • EXAMPLE 14 Substantially Dimethyl Branched Alkylbenzenesulfonic Acid Mixture With Randomized Branching and a 2/3-Phenyl Index of About 200 and 2-Methyl-2-Phenyl Index of About 0.04 (A modified alkylbenzenesulfonic acid mixture in accordance with the invention)
  • the dimethyl branched alkylbenzene product of example 13 is sulfonated with a molar equivalent of chlorosulfonic acid using methylene chloride as solvent with HC1 evolved as a side product.
  • the resulting sulfonic acid product is concentrated by evaporation of methylene chloride under vacuum.
  • the resulting sulfonic acid product has a 2/3-Phenyl Index of about 200 and a 2-methyl-2-phenyl index of about 0.04.
  • EXAMPLE 15 Substantially Dimethyl Branched Alkylbenzene Sulfonic Acid, Sodium Salt Mixture with Randomized Branching and 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of About 0.04 (A modified alkylbenzenesulfonate surfactant mixture in accordance with the invention)
  • the dimethyl branched alkylbenzenesulfonic acid mixture of example 14 is neutralized with a molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give solid dimethyl branched alkylbenzene sulfonate, sodium salt mixture with randomized branching and a 2/3-Phenyl Index of about 200 and a 2-methyl-2- phenyl index of about 0.04.
  • EXAMPLE 16 Mixture of Linear and Branched Alkylbenzenes With a 2/3-Phenyl Index of About 200 and a 2-Methyl-2-Phenyl Index of About 0.01
  • a modified alkylbenzene mixture in accordance with the invention A modified alkylbenzene mixture is prepared by combining 147.5 g of the product of example example 3 and 63.2 g of the product of example 6.
  • the resulting modified alkylbenzene mixture has a 2/3-phenyl index of about 200 and a 2-Methyl-2-phenyl Index of about 0.01.
  • the resulting modified alkylbenzene mixture of example 16 is sulfonated with a molar equivalent of chlorosulfonic acid using methylene chloride as solvent with HC1 evolved as a side product.
  • the resulting sulfonic acid product is concentrated by evaporation of methylene chloride under vacuum.
  • the resulting modified alkylbenzenesulfonic acid product has a 2/3-Phenyl Index of about 200 and a 2-methyl-2 -phenyl index of about 0.01.
  • compositional parameters of conventional linear alkylbenzenes and/or highly branched alkylbenzenesulfonates See, for example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, Volume 73, Chapter 7.
  • this is done by GC and/or GC-mass spectroscopy for the alkylbenzenes and HPLC for the alkylbenzenesulfonates or sulfonic acids; 13 C nmr is also commonly used.
  • Another common practice is desulfonation. This permits GC and/or GC-mass spectroscopy to be used, since desulfonation converts the sulfonates or sulfonic acids to the alkylbenzenes which are tractable by such methods.
  • the present invention provides unique and relatively complex mixtures of alkylbenzenes, and similarly complex surfactant mixtures of alkylbenzenesulfonates and/or alkylbenzenesulfonic acids.
  • Compositional parameters of such compositions can be determined using variations and combinations of the art-known methods.
  • the material contains more than about 10%> impurities such as dialkylbenzenes, olefins, paraffins, hydrotropes, dialkylbenzenesulfonates, etc.
  • Carrier Gas Hydrogen Column Head Pressure: 9 psi Flows: Column Flow @ 1 ml/min. Split Vent @ ⁇ 3ml/min. Septum Purge @ 1 ml/min.
  • Injection HP 7673 Autosampler, 10 ul syringe, lul injection Injector Temperature: 350 °C Detector Temperature: 400 °C Oven Temperature Program: initial 70 °C hold 1 min. rate 1 °C/min. final 180 °C hold 10 min.
  • Standards required for this method are 2-phenyloctane and 2-phenylpentadecane, each freshly distilled to a purity of greater than 98%>. Run both standards using the conditions specified above to define the retention time for each standard.
  • a rentention time range which is the retention time range to be used for characterizing any alkylbenzenes or alkylbenzene mixtures in the context of this invention (e.g., test samples).
  • Test samples pass the GC test provided that greater than 90% of the total GC area percent is within the retention time range defined by the two standards.
  • Test samples that pass the GC test can be used directly in the NMR1 and NMR2 test methods.
  • Test samples that do not pass the GC test must be further purified by distillation until the test sample passes the GC test.
  • the desulfonation method is a standard method described in "The Analysis of Detergents and Detergent Products" by G. F. Longman on pages 197-199. Two other useful descriptions of this standard method are given on page 230-231 of volume 40 of the Surfactant Sience Series edited by T. M. Schmitt: "Analysis of Surfactants” and on page 272 of volume 73 of the Surfactant Science Series: “Anionic Surfactants” edited by John Cross.
  • This is an alternative method to the HPLC method, described herein, for evaluation of the branched and nonbranched alkylbenzenesulfonic acid and/or salt mixtures (Modified Alkylbenzensulfonic acid and or salt Mixtures).
  • the method provides a means of converting the sulfonic acid and/or salt mixture into branched and nonbranched alkylbenzene mixtures which can then be analyzed by means of the GC and NMR methods NMR1 and NMR2 described herein.
  • Mobile phase B Prepare 2000 mL of 60% acetonitrile in HPLC grade water. Filter through an LC eluent membrane filter and degas prior to use.
  • Wash Solutions Transfer 250 ⁇ L of the standard solution to a 1 mL autosampler vial and add 750 ⁇ L of the wash solution. Cap and place in the autosampler tray.
  • Alkylbenzenesulfonic acid or Alkylbenzenesulfonate Weigh 0.10 g of the alkylbenzenesulfonic acid or salt and quantitatively transfer to a 100 mL volumetric flask. Dissolve with 30 mL ACN and dilute to volume with HPLC grade water. Transfer 250 ⁇ L of the standard solution to a 1 mL autosampler vial and add 750 ⁇ L of the sample solution. Cap and place in the autosampler tray. If solution is excessively turbid, filter through 0.45 ⁇ m membrane before transferring to auto-sampler vial. Cap and place in the auto-sampler tray.
  • HPLC System 1. Prime HPLC pump with mobile phase. Install column and column inlet filter and equilibrate with eluent (0.3 mL/min for at least 1 hr.).
  • Mobile phase B 40% H 2 O/60% ACN time 0 min. 100% Mobile phase A 0% Mobile Phase B time 75 min. 5% Mobile phase A 95% Mobile Phase B time 98 min. 5% Mobile phase A 95% Mobile Phase B time 110 min. 100%, Mobile phase A 0% Mobile Phase B time 120 min. 100% Mobile phase A 0% Mobile Phase B Note: A gradient delay time of 5-10 minutes may be needed depending on dead volume of HPLC system.
  • the sample can be further defined by methods NMR 3 and NMR 4. If the alkylbenzenesulfonic acid/salt mixture contains 10% or more of components outside the retention limits defined by the standards then the mixture should be further purified by method HPLC-P or by DE, DIS methods.
  • Alkylbenzenesulfonic acids and/or the salts which contain substantial impurities (10% or greater) are purified by preparative HPLC. See, for example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, Volume 73, Chapter 7. This is routine to one skilled in the art. A sufficient quantity should be purified to meet the requirements of the NMR 3 and NMR 4.
  • Alkylbenzenesulfonic acids and/or the salts which contain substantial impurities (10%> or greater) can also be purified by an LC method (also defined herein as HPLC-P). This procedure is actually preferred over HPLC column prep purification. As much as 500 mg of unpurified MLAS salts can be loaded onto a 10g(60ml) Mega Bond Elut Sep Pak® and with optimized chromatography the purified MLAS salt can be isolated and ready for freeze drying within 2 hours. A 100 mg sample of Modified alkylbenzenesulfonate salt can be loaded onto a 5g(20ml) Bond Elut Sep Pak and ready within the same amount of time.
  • HPLC Waters Model 600E gradient pump, Model 717 Autosampler, Water's
  • DI-H2O Distilled, deionized water from a Millipore, Milli-Q system or equivalent
  • Reservoir A 60/40, H 2 O/C AN with salt and Reservoir B: 40/60,
  • MLAS SAMPLE LOADING/SEPARATION AND ISOLATION 1. Weigh ⁇ 500 mg of sample into a 2 dram vial and add 5 ml of 70/30 H 2 O/ACN. Sonicate and mix well. 2. Load sample onto Bond Elut and with positive pressure from an air source begin separation. Rinse vial with 2 ml (x2) portions of the 70/30 solution and put onto the sep pak. Maintain -1mm of solution at the head of the sep pak.
  • Adjustments in organic modifier concentration may be necessary for optimum separation and isolation.
  • a 5 liter, 3 -necked round bottom flask with 24/40 joints is equipped with a magnetic stir bar.
  • a few boiling chips (Hengar Granules, catalog #136-C) are added to the flask.
  • a 91/2 inch long vigreux condenser with a 24/40 joint is placed in the center neck of the flask.
  • a water cooled condenser is attached to the top of the vigreux condenser which is fitted with a calibrated thermometer.
  • a vacuum receiving flask is attached to the end of the condenser.
  • a glass stopper is placed in one side arm of the 5 liter flask and a calibrated thermometer in the other. The flask and the vigreux condenser are wrapped with aluminum foil.
  • Fraction B is collected from about 90°C to about 155°C as measured by the calibrated thermometer at the top of the vigreux column. Fraction A and pot residues (high boiling) are discarded. Fraction B (1881 g) contains the alkylbenzene mixture of interest. The method can be scaled according to the practitioner's needs provided that sufficient quantity of the alkylbenzene mixture remains after distillation for evaluation by NMR methods NMR1 and NMR2.
  • Salts of alkylbenzenesulfonic acids are acidified by common means such as reaction in a solvent with HC1 or sulfuric acid or by use of an acidic resin such as Amberlyst 15.
  • a 400 mg sample of an alkylbenzene mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1% v/v TMS as reference and placed in a standard NMR tube.
  • the 13 C NMR is run on the sample on a 300 MHz NMR spectrometer using a 20 second recycle time, a 40° 13 C pulse width and gated heteronuclear decoupling. At least 2000 scans are recorded.
  • the region of the 13 C NMR spectrum between about 145.00 ppm to about 150.00 ppm is integrated.
  • the 2/3-Phenyl index of an alkylbenzene mixture is defined by the following equation:
  • a 400 mg sample of an anhydrous alkylbenzene mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1%, v/v TMS as reference and placed in a standard NMR tube.
  • the 13 C NMR is run on the sample on a 300 MHz NMR spectrometer using a 20 second recycle time, a 40° 13 C pulse width and gated heteronuclear decoupling. At least 2000 scans are recorded.
  • the 13 C NMR spectrum region between about 145.00 ppm to about 150.00 ppm is integrated.
  • the 2-methyl-2- phenyl index of an alkylbenzene mixture is defined by the following equation:
  • 2-methyl-2-phenyl index (Integral from about 149.35 ppm to about 149.80 ppm)/(Integral from about 145.00 ppm to about 150.00 ppm).
  • a 400 mg sample of an anhydrous alkylbenzenesulfonic acid mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1%> v/v TMS as reference and placed in a standard NMR tube.
  • the 13 C NMR is run on the sample on a 300 MHz NMR spectrometer using a 20 second recycle time, a 40° 13 C pulse width and gated heteronuclear decoupling. At least 2000 scans are recorded.
  • the 13 C NMR spectrum region between about 152.50 ppm to about 156.90 ppm is integrated.
  • a 400 mg sample of an anhydrous alkylbenzenesulfonic acid mixture is dissolved in 1 ml of anhydrous deuterated chloroform containing 1%, v/v TMS as reference and placed in a standard NMR tube.
  • the 13 C NMR is run on the sample on a 300 MHz NMR spectrometer using a 20 second recycle time, a 40° 13 C pulse width and gated heteronuclear decoupling. At least 2000 scans are recorded.
  • the 13 C NMR spectrum region between about 152.50 ppm to about 156.90 ppm is integrated.
  • the 2-methyl-2- phenyl Index for an alkylbenzenesulfonic acid mixture is defined by the following equation:
  • 2-methyl-2-phenyl index (Integral from about 156.40 ppm to about 156.65 ppm)/(Integral from about 152.50 ppm to about 156.90 ppm).
  • the hand dishwashing compositions are substantially free from alkylbenzene sulfonate surfactants other than the modified alkylbenzene sulfonate surfactant mixture. That is no alkylbenzene sulfonate surfactants other than the modified alkylbenzene sulfonate surfactant mixture are added to the detergent compositions.
  • the hand dishwashing compositions may contain as an additional surfactant at least about 0.1%o, preferably no more than about 10%, more preferably no more than about 5%, more preferably still, no more than about 1%>, of a commercial C ⁇ )-C 14 linear alkylbenzene sulfonate surfactant. It is further preferred that the commercial C ⁇ o-C 14 linear alkylbenzene sulfonate surfactant has a 2/3 phenyl index of from 75 to 160.
  • the hand dishwashing compositions may contain as an additional surfactant at least about 0.1 %>, preferably no more than about 10%, more preferably no more than about 5%, more preferably still, no more than about 1%>, of a commercial highly branched alkylbenzene sulfonate surfactant.
  • a commercial highly branched alkylbenzene sulfonate surfactant for example TPBS or tetrapropylbenzene sulfonate.
  • the present invention encompasses less preferred but sometimes useful embodiments for their normal purposes, such as the addition of useful hydrotrope precursors and or hydrotropes, such as C ⁇ -C 8 alkylbenzenes, more typically toluenes, cumenes, xylenes, naphthalenes, or the sulfonated derivatives of any such materials, minor amounts of any other materials, such as tribranched alkylbenzene sulfonate surfactants, dialkylbenzenes and their derivatives, dialkyl tetralins, wetting agents, processing aids, and the like.
  • hydrotropes it will not be usual practice in the present invention to include any such materials. Likewise it will be understood that such materials, if and when they interfere with analytical methods, will not be included in samples of compositions used for analytical purposes.
  • the hand dishwashing composition which comprises, in said component (iii), at least about 0.1%, preferably no more than about 10%, more preferably no more than about 5%, more preferably still, no more than about 1%>, of a commercial C ⁇ o-C ⁇ 4 linear alkylbenzene sulfonate surfactant;
  • the hand dishwashing composition which comprises, in said component (iii), at least about 0.1%, preferably no more than about 10%>, more preferably no more than about 5%, more preferably still, no more than about 1%, of a commercial highly branched alkylbenzene sulfonate surfactant, (e.g., TPBS or tetrapropylbenzene sulfonate);
  • a commercial highly branched alkylbenzene sulfonate surfactant e.g., TPBS or tetrapropylbenzene sulfonate
  • the hand dishwashing composition which comprises, in said component (iii), a nonionic surfactant at a level of from about 0.5%> to about 25% by weight of said detergent composition, and wherein said nonionic surfactant is a polyalkoxylated alcohol in capped or non-capped form having: - a hydrophobic group selected from linear C]o-C ⁇ 6 alkyl, mid-chain -C 3 branched C ⁇ o-C 16 alkyl, guerbet branched C ⁇ o-C ⁇ 6 alkyl, and mixtures thereof and - a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates 1-15 butoxylates and mixtures thereof, in capped or uncapped form, (when uncapped, there is also present a terminal primary -OH moiety and when capped, there is also present a terminal moiety of the form -OR wherein R is a C]-C 6 hydrocarbyl moiety, optionally comprising a primary or, preferably when present,
  • the hand dishwashing composition which comprises, in said component (iii), an alkyl sulfate surfactant at a level of from about 0.5% to about 25% by weight of said detergent composition, wherein said alkyl sulfate surfactant has a hydrophobic group selected from linear C ⁇ o-C 18 alkyl, mid-chain C ⁇ -C 3 branched C ⁇ o-C ⁇ 8 alkyl, guerbet branched C ⁇ o-C ⁇ 8 alkyl, and mixtures thereof and a cation selected from Na, K and mixtures thereof;
  • the hand dishwashing composition which comprises, in said component (iii), an alkyl(polyalkoxy)sulfate surfactant at a level of from about 0.5% to about 25% by weight of said detergent composition, wherein said alkyl(polyalkoxy)sulfate surfactant has - a hydrophobic group selected from linear C ⁇ o-C ⁇ 6 alkyl, mid- chain C 1 -C 3 branched C ⁇ o-C 16 alkyl, guerbet branched C ⁇ 0 -C ⁇ 6 alkyl, and mixtures thereof and - a (polyalkoxy)sulfate hydrophilic group selected from 1-15 polyethoxysulfate, 1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed poly(ethoxy/propoxy/butoxy)sulfates, and mixtures thereof, in capped or uncapped form; and - a cation selected from Na, K and mixtures thereof; It is prefe ⁇ e
  • the hand dishwashing composition comprises a nonionic surfactant
  • it is a polyalkoxylated alcohol in capped or non-capped form has a hydrophobic group selected from linear C ⁇ o-C ⁇ 6 alkyl, mid-chain C ⁇ -C branched C ⁇ o-C ⁇ 6 alkyl, guerbet branched alkyl, and mixtures thereof; and a hydrophilic group selected from 1-15 ethoxylates, 1-15 propoxylates 1-15 butoxylates and mixtures thereof, in capped or uncapped form.
  • terminal primary - OH moiety When uncapped, there is also present a terminal primary - OH moiety and when capped, there is also present a terminal moiety of the form -OR wherein R is a C ⁇ -C 6 hydrocarbyl moiety, optionally comprising a primary or, preferably when present, a secondary alcohol.
  • the hand dishwashing composition comprises an alkyl sulfate surfactant which has a hydrophobic group selected from linear C ⁇ o-C ⁇ 6 alkyl, mid- chain C1-C 3 branched C ⁇ o-C ⁇ 8 alkyl, guerbet branched C ⁇ o-C ⁇ 6 alkyl, and mixtures thereof and a cation selected from Na, K and mixtures thereof.
  • the hand dishwashing compositions of the present invention can be used or applied by hand and/or can be applied in unitary or freely alterable dosage, or by automatic dispensing means, They can be used in aqueous or non-aqueous cleaning systems. They can have a wide range of pH, for example from about 2 to about 12 or higher, though alkaline detergent compositions having a pH of from about 8 to about 11 are among the prefe ⁇ ed embodiments, and they can have a wide range of alkalinity reserve. Both high-foaming and low-foaming types are encompassed, as well as types for use in all known aqueous and non aqueous consumer product cleaning processes.
  • the hand dishwashing compositions can be in any conventional form, namely, in the form of a liquid, powder, agglomerate, paste, tablet, bar, gel, liqui-gel microemulsion, liquid crystal, or granule.
  • a conventional hand dishwashing adjunct is any material required to transform a composition containing only the minimum essential ingredients (herein the essential modified alkylbenzene sulfonate surfactant mixture) into a composition useful for hand dishwashing.
  • the essential modified alkylbenzene sulfonate surfactant mixture herein the essential modified alkylbenzene sulfonate surfactant mixture.
  • conventional hand dishwashing adjuncts are easily recognizable to those of skill in the art as being absolutely characteristic of cleaning products.
  • Levels of conventional hand dishwashing adjuncts are from about 0.00001% to about 99.9%, by weight of the composition.
  • Use levels of the overall compositions can vary widely depending on the intended application, ranging for example from a few ppm in solution to so-called “direct application” of the neat cleaning composition to the surface to be cleaned.
  • the conventional hand dishwashing adjunct is selected from the group consisting of builders, detersive enzymes, surfactants other than the modified alkyl benzene sulfonate surfactant mixture, typically selected from anionic, cationic, amphoteric, zwitterionic, nonionic and mixtures thereof, at least partially water-soluble or water dispersible polymers, abrasives, bactericides, tarnish inhibitors, dyes, solvents, hydrotropes, perfumes, thickeners, antioxidants, processing aids, suds boosters, suds suppressors, buffers, anti-fungal agents, mildew control agents, insect repellents, anti- co ⁇ osive aids, chelants and mixtures thereof. More preferably the conventional cleaning adjunct comprises one or more of:
  • a conventional hand dishwashing adjuncts is any material required to transform a composition containing only the minimum essential ingredients (herein the essential modified alkylbenzene sulfonate surfactant mixture) into a composition useful for hand dishwashing.
  • the essential modified alkylbenzene sulfonate surfactant mixture herein the essential modified alkylbenzene sulfonate surfactant mixture
  • conventional hand dishwashing adjuncts are easily recognizable to those of skill in the art as being absolutely characteristic of cleaning products.
  • adjuncts include builders, surfactants, enzymes, and polymers, and the like.
  • Other adjuncts herein can include suds boosters, suds suppressors (antifoams) and the like, diverse active ingredients or specialized materials such as dispersant polymers (e.g., from BASF Co ⁇ . or Rohm & Haas), color speckles, silvercare, anti-tarnish and/or anti-co ⁇ osion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti- oxidants, enzyme stabilizing agents, pro-perfumes, perfumes, solubilizing agents, carriers, processing aids, pigments, and, for liquid formulations, solvents, as described in detail hereinafter.
  • dispersant polymers e.g., from BASF Co ⁇ . or Rohm & Haas
  • color speckles e.g., from BASF Co ⁇ . or Rohm & Haas
  • silvercare e.g., from BASF Co ⁇ .
  • compositions herein may require several adjuncts, though certain simply formulated productsmay require only, one adjunct.
  • a comprehensive list of suitable laundry or cleaning adjunct materials and methods can be found in US Provisional Patent application No. 60/053,318 filed July 21, 1997 and assigned to Procter & Gamble.
  • the modifed alkyl benzene sulfonate surfactants of the present invention can be used in a wide range of hand dishwashing formulations.
  • This novel surfactant system can be used as a total or partial replacement of conventional LAS in existing hand dishwashing compositions.
  • Detersive surfactants - The instant compositions desirably include a detersive surfactant used as a co-surfactant with the essential surfactant mixtures. Since the present invention is surfactant-related, in the descriptions of the prefe ⁇ ed embodiments of the detergent compositions of the invention, surfactant materials are described and accounted for separately from nonsurfactant adjuncts. Detersive surfactants are extensively illustrated in U.S. 3,929,678, Dec. 30, 1975 Laughlin, et al, and U.S. 4,259,217, March 31, 1981, Mu ⁇ hy; in the series “Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R.
  • the detersive surfactant herein includes anionic, nonionic, cationic, zwitterionic or amphoteric types of surfactant known for use as cleaning agents, but does not include completely foam-free or completely insoluble surfactants (though these may be used as optional adjuncts).
  • detersive surfactants useful herein suitably include: (1) conventional alkylbenzene sulfonates, including the hard (ABS, TPBS) or linear types and made by known processe such as various HF or solid HF e.g., DETAL® (UOP) process, or made by using other Lewis Acid catalysts e.g., A1C1 3 , or made using acidic silica/alumina or made from chlorinated hydrocarbons; (2) olefin sulfonates, including ⁇ - olefin sulfonates and sulfonates derived from fatty acids and fatty esters; (3) alkyl or alkenyl sulfosuccinates, including the diester and half-ester types as well as sulfosuccinamates and other sulfonate/ carboxylate surfactant types such as the sulfosuccinates derived from ethoxylated alcohols and alkanolamides
  • more unusual surfactant types are included, such as: (50) alkylamidoamine oxides, carboxylates and quaternary salts; (51) sugar- derived surfactants modeled after any of the hereinabove-referenced more conventional nonsugar types; (52) fluorosurfactants; (53) biosurfactants; (54) organosilicon or fluorocarbon surfactants; (55) gemini surfactants, other than the above-referenced diphenyl oxide disulfonates, including those derived from glucose; (56) polymeric surfactants including amphopolycarboxyglycinates; and (57) bolaform surfactants; in short any surfactant known for aqueous or nonaqueous cleaning.
  • hydrophobe chain length is typically in the general range C ⁇ -C20 > with chain lengths in the range C ⁇ -Ci8 often being prefe ⁇ ed, especially when laundering is to be conducted in cool water. Selection of chainlengths and degree of alkoxylation for conventional pu ⁇ oses are taught in the standard texts.
  • the detersive surfactant is a salt
  • any compatible cation may be present, including H (that is, the acid or partly acid form of a potentially acidic surfactant may be used), Na, K, Mg, ammonium or alkanolammonium, or combinations of cations.
  • detersive surfactants having different charges are commonly prefe ⁇ ed, especially anionic/cationic, anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures.
  • any single detersive surfactant may be substituted, often with desirable results for cool water washing, by mixtures of otherwise similar detersive surfactants having differing chainlengths, degree of unsaturation or branching, degree of alkoxylation (especially ethoxylation), insertion of substituents such as ether oxygen atoms in the hydrophobes, or any combinations thereof.
  • Prefe ⁇ ed among the above-identified detersive surfactants are: acid, sodium and ammonium C9-C20 linear alkylbenzene sulfonates, particularly sodium linear secondary alkyl C10-C15 benzenesulfonates though in some regions ABS may be used (1); olefmsulfonate salts, (2), that is, material made by reacting olefins, particularly C10-C2O ⁇ -olefms, with sulfur trioxide and then neutralizing and hydrolyzing the reaction product; sodium and ammonium C7-C12 dialkyl sulfosuccinates, (3); alkane monosulfonates, (4), such as those derived by reacting C8-C20 cc-olefms with sodium bisulfite and those derived by reacting paraffins with SO2 and CI2 and then hydrolyzing with a base to form a random sulfonate; ⁇ -Sulfo fatty acid
  • Such compounds when branched can be random or regular.
  • they When secondary, they preferably have formula CH3(CH2) x (CHOSO3 " M ) CH3 or CH3(CH 2 )y(CHOSO3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least 7, preferably at least 9 and M is a water-soluble cation, preferably sodium.
  • sulfates such as oleyl sulfate are prefe ⁇ ed, while the sodium and ammonium alkyl sulfates, especially those produced by sulfating C8-C18 alcohols, produced for example from tallow or coconut oil are also useful; also prefe ⁇ ed are the alkyl or alkenyl ether sulfates, (16), especially the ethoxy sulphates having about 0.5 moles or higher of ethoxylation, preferably from 0.5-8; the alkylethercarboxylates, (19), especially the EO 1- 5 ethoxycarboxylates; soaps or fatty acids (21), preferably the more water-soluble types; aminoacid-type surfactants, (23), such as sarcosinates, especially oleyl sarcosinate; phosphate esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), especially the e
  • Cationic surfactants suitable for use in the present invention include those having a long-chain hydrocarbyl group.
  • cationic co-surfactants include the ammonium co-surfactants such as alkyldimethylammonium halogenides, and those co- surfactants having the formula:
  • R ⁇ is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R- is selected from the group consisting of -CH2CH2-, CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of -C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2CHOH- CHOHCOR CHOHCH2OH wherein R ⁇ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R ⁇ is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R ⁇ plus R ⁇ is
  • Suitable cationic surfactants are those co ⁇ esponding to the general formula:
  • R ⁇ , R2, R3, and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt- forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate radicals.
  • the aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups.
  • the longer chain aliphatic groups e.g., those of about 12 carbons, or higher, can be saturated or unsaturated.
  • Prefe ⁇ ed is when R ⁇ , R2, R3, and R4 are independently selected from Cl to about C22 alkyl.
  • Especially prefe ⁇ ed are cationic materials containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains.
  • the long alkyl chains in the compounds described in the previous sentence have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short alkyl chains in the compounds described in the previous sentence have from 1 to about 3 carbon atoms, preferably from 1 to about 2 carbon atoms.
  • Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%, preferably from about 1%> to about 15%, although much higher levels, e.g., up to about 30%) or more, may be useful especially in nonionic: cationic (i.e., limited or anionic-free) formulations.
  • cationic surfactants is as grease release agents.
  • Cationic surfactants can be on their own or in combination with solvents and/or solublizing agents. See US Patent 5552089.
  • dianionics are surfactants which have at least two anionic groups present on the surfactant molecule.
  • dianionic surfactants are further described in copending U.S. Serial No. 60/020,503 (Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832 (Docket No. 6159P) and 60/020,773 (Docket No. 6162P) all filed on June 28, 1996, and 60/023,539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), 60/023,540 (Docket No. 6193P) and 60/023,527 (Docket No. 6195P) filed on August 8th, 1996, the disclosures of which are inco ⁇ orated herein by reference.
  • the surfactant may be a midchain branched alkyl sulfate, midchain branched alkyl alkoxylate, or midchain branched alkyl alkoxylate sulfate.
  • These surfactants are further described in No. 60/061,971, Attorney docket No 6881P October 14, 1997, No. 60/061,975, Attorney docket No 6882P October 14, 1997, No. 60/062,086, Attorney docket No 6883P October 14, 1997, No. 60/061,916, Attorney docket No 6884P October 14, 1997, No. 60/061,970, Attorney docket No 6885P October 14, 1997, No.
  • 60/062,407 Attorney docket No 6886P October 14, 1997,.
  • Other suitable mid-chain branched surfactants can be found in U.S. Patent applications Serial Nos. 60/032,035 (Docket No. 6401P), 60/031,845 (Docket No. 6402P), 60/031,916 (Docket No. 6403P), 60/031,917 (Docket No. 6404P), 60/031,761 (Docket No. 6405P), 60/031,762 (Docket No. 6406P) and 60/031,844 (Docket No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions.
  • Rl is a Cn alkyl group
  • R2 is H or is a Cm alkyl group, with n+m being a number from 11-14;
  • modified alkylbenzene sulfonate surfactant is with a monoalkyl succinamate, more preferably with from about 0.5 to about 6% by weight of a Cio to C ⁇ 8 monoalkyl succinamate, wherein the alkyl group may be ethoxylated with up to 8 moles of ethylene oxide, the monoalkyl succinamate has the structure:
  • R is an aliphatic radical, of from 10 to 18 carbon atoms
  • M is a cation, selected from the group consisting of sodium, potassium, ammonium and alkanolamine. See US Patent 5480586.
  • Suitable levels of anionic detersive surfactants herein are in the range from about 1% to about 50%, or higher, preferably from about 2%> to about 30%, more preferably still, from about 5% to about 20% by weight of the detergent composition.
  • Suitable levels of nonionic detersive surfactant herein are from about 1% to about 40%), preferably from about 2%> to about 30%, more preferably from about 5%, to about 20%.
  • Desirable weight ratios of anionic : nonionic surfactants in combination include from 1.0:9.0 to 1.0:0.25, preferably 1.0:1.5 to 1.0:0.4.
  • Desirable weight ratios of anionic : cationic surfactants in combination include from 50:1 to 5:1, more preferably 35:1 to 15:1.
  • Suitable levels of cationic detersive surfactant herein are from about 0.1 %> to about 20%, preferably from about 1% to about 15%, although much higher levels, e.g., up to about 30%) or more, may be useful especially in nonionic : cationic (i.e., limited or anionic-free) formulations.
  • Amphoteric or zwitterionic detersive surfactants when present are usually useful at levels in the range from about 0.1%, to about 20% by weight of the detergent composition. Often levels will be limited to about 5% or less, especially when the amphoteric is costly.
  • the composition will preferably contain at least about 0.01%,, more preferably at least about 0.1 %, even more preferably still, at least about 0.2%>, even more preferably still, at least about 0.5% by weight of said composition of surfactant.
  • the composition will also preferably contain no more than about 90%, more preferably no more than about 70%, even more preferably, no more than about 60%, even more preferably, no more than about 35% by weight of said composition of surfactant.
  • the anionic surfactants useful in the present invention are preferably selected from the group consisting of, linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof.
  • anionic surfactant When present, anionic surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.5%, more preferably at least about 5%, even more preferably still, at least about 10% by weight of said composition of anionic surfactant. The composition will also preferably contain no more than about 90%, more preferably no more than about 50%, even more preferably, no more than about 30%> by weight of said composition of anionic surfactant.
  • Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein.
  • dissolution of alkyl sulfates can be obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably
  • alkyl chains of C12-16 are prefe ⁇ ed for lower wash temperatures (e.g., below about 50°C) and C16-18 alkyl chains are prefe ⁇ ed for higher wash temperatures (e.g., above about 50°C).
  • Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl- ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium.
  • Surfactants for use herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching.
  • the anionic surfactant component may comprise alkyl sulfates and alkyl ether sulfates derived from conventional alcohol sources, e.g., natural alcohols, synthetic alcohols such as those sold under the trade name of NEODOLTM, ALFOLTM, LIALTM, LUTENSOLTM and the like.
  • Alkyl ether sulfates are also known as alkyl polyethoxylate sulfates.
  • Suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • alkyl ester sulfonates are desirable because they can be made with renewable, non-petroleum resources.
  • Preparation of the alkyl ester sulfonate surfactant component can be effected according to known methods disclosed in the technical literature. For instance, linear esters of C8-C20 carboxylic acids can be sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
  • the prefe ⁇ ed alkyl ester sulfonate surfactant comprises alkyl ester sulfonate surfactants of the structural formula: wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble salt- forming cation.
  • Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, - trimethyl, and quaternary ammonium cations, e.g.
  • R3 is C10-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C14-C16 alkyl.
  • anionic surfactants useful for detersive pu ⁇ oses can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefmsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C9-C20 linear alkylbenzenesulphonates C8-C22 primary or secondary alkanesulphonates
  • alkyl glycerol sulfonates 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12- C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpol
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are generally disclosed in U.S.
  • exemplary, non- limiting classes of useful nonionic surfactants include: alkyl ethoxylate, alkanoyl glucose amide, C12 -C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), and mixtures thereof.
  • nonionic surfactant When present, nonionic surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.1 %, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of nonionic surfactant. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%,, even more preferably, no more than about 10% by weight of said composition of nonionic surfactant.
  • the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are prefe ⁇ ed. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Co ⁇ oration; and Triton® X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. These compounds are commonly refe ⁇ ed to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Particularly prefe ⁇ ed are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a na ⁇ ow molecular weight distribution), both marketed by Union Carbide Co ⁇ oration; Neodol® 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter
  • nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is refe ⁇ ed to generally as "alkyl ethoxylates.”
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50%, of the total weight of the condensation product, which co ⁇ esponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available Pluronic® surfactants, marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80%> by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF.
  • the prefe ⁇ ed alkylpolyglycosides have the formula
  • R2O(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3- , 4- and/or 6-position, preferably predominantly the 2-position.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the prefe ⁇ ed alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.
  • ethoxylated glycerol type compound a mixture of a fully esterified ethoxylated polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol, wherein the prefe ⁇ ed polyhydric alcohol is glycerol, and the compound is
  • B is selected from the group consisting of hydrogen or a group represented by:
  • R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most prefe ⁇ ed, wherein at least one of the B groups is represented by said
  • O '/ C-R' and R' is selected from the group consisting of hydrogen and methyl groups;
  • x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that (x+y+z) equals 2 to 100, preferably 4 to 24 and most preferably 4 to 19, wherein in Formula (I) the wt. ratio of monoester/diester/triester is 45 to 90/5 to 40/1 to 20, more preferably 50 to 90/9 to 32/1 to 12, wherein the wt. ratio of Formula (I) to Formula (II) is a value between 3 to
  • the ethoxylated glycerol type compound which may be used in the in the instant composition are manufactured by the Kao Co ⁇ oration and sold under the trade name
  • Levenol such as Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to glycerol of 0.55 or Levenol V501/2 which has an average EO of 17 and a molar ratio of tallow fatty acid to glycerol of 1.0. It is prefe ⁇ ed that the molar ratio of the fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than 1.0.
  • the ethoxylated glycerol type compound has a molecular weight of 400 to
  • the Levenol compounds are substantially non irritant to human skin and have a primary biodegradabillity higher than
  • Levenol V-501/2 which has 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465
  • Levenol F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
  • Both Levenol F-200 and Levenol V-501/2 are composed of a mixture of Formula (I) and Formula (II).
  • the Levenol compounds has ecoxicity values of algae growth inhibition >100 mg/liter; acute toxicity for Daphniae >100 mg/liter and acute fish toxicity >100 mg/liter.
  • the Levenol compounds have a ready biodegradability higher than 60% which is the minimum required value according to OECD 301B measurement to be acceptably biodegradable.
  • Polyesterified nonionic compounds also useful in the instant compositions are Crovol PK-40 and Crovol PK-70 manufactured by Croda GMBH of the Netherlands.
  • Crovol PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which has 12 EO groups.
  • Crovol PK-70 which is prefe ⁇ ed is a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups. More information on these nonionic surfactants can be found in US Patents No 5719114,
  • Suitable nonionic surfactant comprises the polyhydroxy fatty acid amides. These materials are more fully described in Pan/Gosselink; U.S Patent 5,332,528; Issued July 26, 1994, which is inco ⁇ orated herein by reference. These polyhydroxy fatty acid amides have a general structure of the formula:
  • Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n-l- CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most prefe ⁇ ed are glycityls wherein n is 4, particularly -CH2- (CHOH)4-CH2OH.
  • R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2- hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive animation reaction to form a co ⁇ esponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
  • Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
  • surfactants include the C10-C18 N-methyl, or N-hydroxypropyl, glucamides.
  • the N-propyl through N-hexyl C12-C16 glucamides can be used for lower sudsing performance.
  • Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
  • alkanol amide surfactants including the ammonia, monoethanol, and diethanol amides of fatty acids having an acyl moiety containing from about 8 to about 18 carbon atoms. These materials are represented by the formula:
  • Rl is a saturated or unsaturated, hydroxy-free aliphatic hydrocarbon group having from about 7 to 21, preferably from about 11 to 17 carbon atoms;
  • R2 represents a methylene or ethylene group; and
  • m is 1, 2, or 3, preferably 1.
  • Specific examples of such amides are monoethanol amine coconut fatty acid amide and diethanolamine dodecyl fatty acid amide.
  • These acyl moieties may be derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil, and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • the monoethanolamides and diethanolamides of C 12- 14 fatty acids are prefe ⁇ ed.
  • Amphoteric Surfactants may optionally be inco ⁇ orated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No.
  • Prefe ⁇ ed amphoteric include C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and mixtures thereof.
  • amphoteric surfactant When present, amphoteric surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.1 %, more preferably at least about 0.2%, even more preferably still, at least about 0.5% by weight of said composition of amphoteric surfactant. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%), even more preferably, no more than about 10% by weight of said composition of amphoteric surfactant.
  • Amine oxides are amphoteric surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Prefe ⁇ ed amine oxide surfactants have the formula
  • R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms
  • R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof
  • x is from 0 to about 3
  • each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C10-C18 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • amine oxide surfactant When present, amine oxide surfactant will be present typically in an effective amount. More preferably, the composition may contain at least about 0.1 %, more preferably at least about 0.2%), even more preferably still, at least about 0.5% by weight of said composition of amine oxide surfactant. The composition will also preferably contain no more than about 20%, more preferably no more than about 15%, even more preferably, no more than about 10% by weight of said composition of amine oxide surfactant.
  • amine oxide surfactants examples include "Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).
  • Suitable betaine surfactants include those of the general formula: wherein R is a hydrophobic group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amino or ether linkages; each Rl is an alkyl group containing from 1 to about 3 carbon atoms; and R2 is an alkylene group containing from 1 to about 6 carbon atoms.
  • prefe ⁇ ed betaines examples include dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.
  • Other suitable amidoalkylbetaines are disclosed in U.S. Patent Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236, all of which are inco ⁇ orated herein by reference.
  • Zwitterionic Surfactants - Zwitterionic surfactants can also be inco ⁇ orated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants. Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • Detersive Enzymes - Enzymes are preferably included in the present detergent compositions for a variety of pu ⁇ oses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates.
  • Recent enzyme disclosures in detergents useful herein include chondriotinase ( EP 747,469 A); protease variants ( WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO 96/25489 A); xylanase ( EP 709,452 A); keratinase (EP 747,470 A); lipase ( GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A); thermitase (WO 96/28558
  • suitable enzymes include cellulases, hemicellulases, proteases, gluco- amylases, amylases, Upases, cutinases, pectinases, xylanases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, chondriotinases, thermitases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Prefe ⁇ ed selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are prefe ⁇ ed, such as bacterial amylases and proteases, and fungal cellulases.
  • a prefe ⁇ ed combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and or cellulase. Suitable enzymes are also described in US Patent Nos.
  • the composition will preferably contain at least about 0.0001%, more preferably at least about 0.0005%, even more preferably still, at least about 0.001%> by weight of the composition of enzyme.
  • the cleaning composition will also preferably contain no more than about 5%, more preferably no more than about 2%, even more preferably, no more than about 1% by weight of the composition of enzyme.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in cleaning compositions.
  • Prefe ⁇ ed detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Highly prefe ⁇ ed are amylases and/or proteases, including both cu ⁇ ent commercially available types and improved types.
  • Enzymes are normally inco ⁇ orated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
  • the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1%> by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteolytic Enzyme can be of animal, vegetable or microorganism (prefe ⁇ ed) origin.
  • the proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-type proteases.
  • Prefe ⁇ ed for use herein are subtilisin-type proteolytic enzymes.
  • Particularly prefe ⁇ ed is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable proteolytic enzymes include Novo Industri A/S Alcalase® (prefe ⁇ ed), Esperase®' Savinase® (Copenhagen, Denmark), Gist-brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN'(prefe ⁇ ed), which are commercially available.
  • Prefe ⁇ ed proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European Patent 251,446B, granted December 28, 1994 (particularly pages 17, 24 and 98) and which are also called herein "Protease B".
  • Protease A a modified bacterial serine proteolytic enzyme
  • BPN' modified bacterial serine proteolytic enzyme
  • Prefe ⁇ ed proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention.
  • Another prefe ⁇ ed protease, refe ⁇ ed to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described
  • proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • Protease enzyme may be inco ⁇ orated into the compositions in accordance with the invention at a level of from 0.0001% to 2%> active enzyme by weight of the composition.
  • the composition will preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%>, even more preferably still, at least about 0.001%> of active enzyme by weight of the composition of protease enzyme.
  • the composition will also preferably contain no more than about 2% > , more preferably no more than about 0.5%>, more preferably no more than about 0.1 %, even more preferably, no more than about 0.05%> of active enzyme by weight of the composition of protease enzyme.
  • Amylase - Amylases ( ⁇ and or ⁇ ) can be included for removal of carbohydrate-based stains.
  • Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk).
  • the enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • the composition will preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably still, at least about 0.001%> of active enzyme by weight of the composition of amylase enzyme.
  • the composition will also preferably contain no more than about 2%>, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of amylase enzyme.
  • Amylase enzymes also include those described in WO95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056.
  • Other specific amylase enzymes for use in the detergent compositions of the present invention therefore include :
  • ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 °C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO95/26397.
  • ⁇ -amylases according (a) comprising the amino sequence shown in the SEQ ID listings in the above cited reference, or an ⁇ -amylase being at least 80% homologous with the amino acid sequence shown in the SEQ ID listing.
  • ⁇ -amylases according (a) obtained from an alkalophilic Bacillus species, comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr- Met-Met-Gln-Tyr-Phe-Glu-T ⁇ -Tyr-Leu-Pro-Asn-Asp.
  • a polypeptide is considered to be X%> homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%
  • ⁇ -amylases according (a-c) wherein the ⁇ -amylase is obtainable from an alkalophilic Bacillus species; and in particular, from any of the strains NCIB 12289, NCIB 12512, NOB 12513 and DSM 935.
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.
  • (e) ⁇ -amylase showing positive immunological cross-reactivity with antibodies raised against an ⁇ -amylase having an amino acid sequence co ⁇ esponding respectively to those ⁇ -amylases in (a-d).
  • Variants of the following parent ⁇ -amylases which (i) have one of the amino acid sequences shown in co ⁇ esponding respectively to those ⁇ -amylases in (a-e), or (ii) displays at least 80%> homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hybridizes with the same probe as a DNA sequence encoding an ⁇ -amylase having one of said amino acid sequence; in which variants :
  • At least one amino acid residue of said parent ⁇ -amylase has been replaced by a different amino acid residue
  • At least one amino acid residue has been inserted relative to said parent ⁇ - amylase; said variant having an ⁇ -amylase activity and exhibiting at least one of the following properties relative to said parent ⁇ -amylase : increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or ⁇ -amylolytic activity at neutral to relatively high pH values, increased ⁇ -amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ - amylase variant to the pH of the medium.
  • amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521.
  • Certain prefe ⁇ ed embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use in 1993.
  • oxidative stability e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10
  • thermal stability e.g., at common wash temperatures such as about 60°C
  • alkaline stability e.g., at a pH from about 8 to about 11 , measured versus the above-identified reference-point amylase.
  • Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597.
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly prefe ⁇ ed amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability- enhanced amylases vs. the above-identified reference amylase are prefe ⁇ ed for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such prefe ⁇ ed amylases include (a) an amylase according to the hereinbefore inco ⁇ orated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.
  • Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly prefe ⁇ ed amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee,
  • oxidative stability enhanced amylase examples include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other prefe ⁇ ed enzyme modifications are accessible. See WO 9509909 A to Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • CAREZYME® and CELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo.
  • the composition will preferably contain at least about 0.0001%, more preferably at least about 0.0002%, more preferably at least about 0.0005%, even more preferably still, at least about 0.001% of active enzyme by weight of the composition of cellulases and or peroxidases enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of cellulases and or peroxidases enzyme.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
  • Lipase - Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter refe ⁇ ed to as "Amano-P".
  • Further suitable lipases are lipases such as Ml
  • Lipase® and Lipomax® are suitable commercial lipases.
  • suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Highly prefe ⁇ ed lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • D native lipase ex Humicola lanuginosa aspartic acid
  • L Leucine
  • the substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • the lipase variant may be added in an amount co ⁇ esponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor.
  • the composition will preferably contain at least about 0.0001%), more preferably at least about 0.0002%>, more preferably at least about 0.0005%), even more preferably still, at least about 0.001%, of active enzyme by weight of the composition of lipase enzyme.
  • the composition will also preferably contain no more than about 2%, more preferably no more than about 0.5%,, more preferably no more than about 0.1%, even more preferably, no more than about 0.05% of active enzyme by weight of the composition of lipase enzyme.
  • carbohydrase enzymes which impart antimicrobial activity may also be included in the present invention.
  • Such enzymes include endoglycosidase, Type II endoglycosidase and glucosidase as disclosed in U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 the disclosures of which are herein inco ⁇ orated by reference.
  • other enzymes having antimicrobial activity may be employed as well including peroxidases, oxidases and various other enzymes.
  • a range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their inco ⁇ oration into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • Enzyme Stabilizing System -_The prefe ⁇ ed compositions herein may additionally comprise from about 0.001% to about 10%,, preferably from about 0.005% to about 8%>, most preferably from about 0.01% to about 6%>, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the protease or other enzymes used in the compositions herein.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof such as are described in U.S.
  • the composition will preferably contain at least about 0.001 %>, more preferably at least about 0.005%>, even more preferably still, at least about 0.01% by weight of the composition of enzyme stabilizing system.
  • the composition will also preferably contain no more than about 10%, more preferably no more than about 8%, no more than about 6% of active enzyme by weight of the composition of enzyme stabilizing system.
  • One stabilizing approach is the use of water-soluble sources of calcium and or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are prefe ⁇ ed herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes inco ⁇ orated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts co ⁇ esponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant. However, it is especially prefe ⁇ ed that the composition contain no added calcium ions, and even more prefe ⁇ ed that the composition be free of calcium ions.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboronic acid, p- bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.
  • chlorine bleach or oxygen bleach scavengers can be added to compositions of the present invention to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbonate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • antioxidants like carbonate, ascorbate, etc.
  • organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • Builders - Detergent builders are optionally included in the compositions herein. In solid formulations, builders sometimes serve as absorbents for surfactants. Alternately, certain compositions can be formulated with completely water-soluble builders, whether organic or inorganic, depending on the intended use.
  • Suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amo ⁇ hous-solid silicates or other types, for example especially adapted for use in non- structured-liquid detergents.
  • Prefe ⁇ ed are alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1, including solid hydrous 2-ratio silicates marketed by PQ Co ⁇ . under the tradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck.
  • NaSKS-6 is a crystalline layered aluminum- free ⁇ -Na2Si ⁇ 5 mo ⁇ hology silicate marketed by Hoechst and is prefe ⁇ ed especially in granular compositions. See preparative methods in German DE-A-3 ,417,649 and DE-A- 3,742,043.
  • Other layered silicates such as those having the general formula NaMSi x ⁇ 2 ⁇ +l-yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein.
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ , ⁇ and ⁇ layer-silicate forms.
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, and as a component of suds control systems.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2O-ySiO2.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
  • Aluminosilicate builders such as zeolites, are especially useful in granular detergents, but can also be inco ⁇ orated in liquids, pastes or gels.
  • Suitable for the present pu ⁇ oses are those having empirical formula: [M z (Al ⁇ 2) z (Si ⁇ 2) v ]-xH2 ⁇ wherein z and v are integers of at least 6, M is an alkali metal, preferably Na and/or K, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amo ⁇ hous, naturally-occurring or synthetically derived.
  • aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976.
  • Prefe ⁇ ed synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP.
  • Natural types, including clinoptilolite, may be used.
  • Zeolite A has the formula: Nai 2[(AlO2)i2(SiO2)i2]"xH2O wherein x is from 20 to 30, especially 27.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Detergent builders in place of or in addition to the silicates and aluminosilicates described hereinbefore can optionally be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned.
  • Builder level can vary widely depending upon end use and physical form of the composition.
  • Built detergents typically comprise at least about 1% builder.
  • Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder.
  • Granular formulations typically comprise from about 10%> to about 80%>, more typically 15%) to 50%, builder by weight of the detergent composition.
  • Lower or higher levels of builders are not excluded.
  • certain formulations can be unbuilt, that is the compositions contain no builder such as in some hand dishwashing compositions.
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • phosphates and polyphosphates especially the sodium salts
  • carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxy
  • borates e.g., for pH-buffering pu ⁇ oses
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH- buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
  • prefe ⁇ ed builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1 :80.
  • Certain prefe ⁇ ed laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0.
  • P-containing detergent builders often prefe ⁇ ed where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds.
  • Suitable "organic detergent builders”, as described herein for use in the cleaning compositions include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are prefe ⁇ ed.
  • Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S.
  • organic detergent builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrates e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for light duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.
  • alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 -hydroxy- 1,1- diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscaling properties.
  • detersive surfactants or their short-chain homologues also have a builder action.
  • these materials are summed up as detersive surfactants.
  • Prefe ⁇ ed types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986.
  • Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
  • Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C12-C1 monocarboxyhc acids, can also be inco ⁇ orated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
  • Mineral Builders examples of these builders, their use and preparation can be found in US Patent 5,707,959.
  • Another suitable class of inorganic builders are the Magnesiosilicates, see WO97/0179.
  • Suitable polycarboxylates builders for use herein include maleic acid, citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C 12- 16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Mixtures of these suitable polycarboxylates builders is also envisioned, such as a mixture of maleic acid and citric acid. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated CIO- 18 fatty acids, as well as the co ⁇ esponding soaps.
  • Prefe ⁇ ed saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the prefe ⁇ ed unsaturated fatty acid is oleic acid.
  • Other prefe ⁇ ed builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • the composition will preferably contain at least about 0.2%,, more preferably at least about 0.5%, more preferably at least about 3%, even more preferably still, at least about 5% by weight of the composition of builder.
  • the cleaning composition will also preferably contain no more than about 50%, more preferably no more than about 40%>, more preferably no more than about 30%, even more preferably, no more than about 25%) by weight of the composition of builder.
  • Divalent Ions The presence of magnesium (divalent) ions improves the cleaning of greasy soils for various compositions, i.e., compositions containing alkyl ethoxy sulfates and/or polyhydroxy fatty acid amides. This is especially true when the compositions are used in softened water that contains few divalent ions. It is believed, while not wanting to be limited by theory, that, magnesium ions increase the packing of the surfactants at the oil/water interface, thereby reducing interfacial tension and improving grease cleaning. Compositions of the invention herein containing magnesium ions exhibit good grease removal, manifest mildness to the skin, and provide good storage stability.
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.015%, more preferably at least about 0.02%>, even more preferably still, at least about 0.025% by weight of said composition of divalent ions,.
  • the cleaning composition will also preferably contain no more than about 5%>, more preferably no more than about 2.5%, more preferably no more than about 1%, even more preferably, no more than about 0.05% by weight of said composition of divalent ions
  • the divalent ions, ions are added as a hydroxide, chloride, acetate, formate, oxide or nitrate salt to the compositions of the present invention. It is prefered that when the compositions of the present invention include diavlaent ions, that the divalent ions be magnesium ions.
  • divalent ion-containing compositions in alkaline pH matrices may be difficult due to the incompatibility of the divalent ions, particularly magnesium, with hydroxide ions.
  • divalent ions and alkaline pH are combined with the surfactant mixture of this invention, grease cleaning is achieved that is superior to that obtained by either alkaline pH or divalent ions alone.
  • the stability of these compositions becomes poor due to the formation of hydroxide precipitates. Therefore, chelating agents discussed hereinafter may also be necessary.
  • the diamines are over 95%) pure, i.e., preferably 97%>, more preferably 99%, still more preferably 99.5%, free of impurities.
  • impurities which may be present in commercially supplied diamines include 2-Methyl-l,3-diaminobutane and alkylhydropyrimidine.
  • the diamines should be free of oxidation reactants to avoid diamine degradation and ammonia formation. Additionally, if amine oxide and/or other surfactants are present, the amine oxide or surfactant should be hydrogen peroxide-free.
  • the prefe ⁇ ed level of hydrogen peroxide in the amine oxide or surfactant paste of amine oxide is 0-40 ppm, more preferably 0-15 ppm.
  • Amine impurities in amine oxide and betaines, if present, should be minimized to the levels refe ⁇ ed above for hydrogen peroxide.
  • compositions free of hydrogen peroxide is important when the compositions contain an enzyme.
  • the peroxide can react with the enzyme and destroy any performance benefits the enzyme adds to the composition. Even small amounts of hydrogen peroxide can cause problems with enzyme containing formulations.
  • the diamine can react with any peroxide present and act as an enzyme stabilizer and prevent the hydrogen peroxide from reacting with the enzyme. The only draw back of this stabilization of the enzymes by the diamine is that the nitrogen compounds produced are believed to cause the malodors which can be present in diamine containing compositions. Having the diamine act as an enzyme stabilizer also prevents the diamine from providing the benefits to the composition for which it was originally put in to perform, namely, grease cleaning, sudsing, dissolution and low temperature stability.
  • compositions of the present invention be "malodor" free. That is, that the odor of the headspace does not generate a negative olfactory response from the consumer.
  • This can be achieved in many ways, including the use of perfumes to mask any undesirable odors, the use of stabilizers, such as antioxidants, chelants etc., and/or the use of diamines which are substantially free of impurities. It is believed, without wanting to being limited by theory, that it is the impurities present in the diamines that are the cause of most of the malodors in the compositions of the present invention. These impurities can form during the preparation and storage of the diamines. They can also form during the preparation and storage of the inventive composition.
  • stabilizers such as antioxidants and chelants inhibit and/or prevent the formation of these impurities in the composition from the time of preparation to ultimate use by the consumer and beyond. Hence, it is most prefe ⁇ ed to remove, suppress and/or prevent the formation of these malodors by the addition of perfumes, stabilizers and/or the use of diamines which are substantially free from impurities.
  • prefe ⁇ ed organic diamines are those in which pKl and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, even more preferably from about 8.6 to about 10.75.
  • Other prefe ⁇ ed materials are the primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and
  • pKal and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from “Critical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by Dupont, a supplier of diamines.
  • the pKa of the diamines is specified in an all- aqueous solution at 25oC and for an ionic strength between 0.1 to 0.5 M.
  • the pKa is an equilibrium constant which can change with temperature and ionic strength; thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions.
  • the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines”.
  • diamines useful herein can be defined by the following structure:
  • R2-5 are independently selected from H, methyl, -CH3CH2, and ethylene oxides;
  • Cx and Cv are independently selected from methylene groups or branched alkyl groups where x+y is from about 3 to about 6; and
  • A is optionally present and is selected from electron donating or withdrawing moieties chosen to adjust the diamine pKa's to the desired range. If A is present, then x and y must both be 1 or greater.
  • the diamines can be those organic diamines with a molecular weight less than or equal to 400 g/mol. It is prefe ⁇ ed that these diamines have the formula:
  • each R6 is independently selected from the group consisting of hydrogen, C1-C4 linear or branched alkyl, alkyleneoxy having the formula:
  • R7 is C2-C4 linear or branched alkylene, and mixtures thereof;
  • R8 is hydrogen, C1-C4 alkyl, and mixtures thereof;
  • m is from 1 to about 10;
  • X is a unit selected from: i) C3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene, C3-C10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula: - ⁇ ?O - wherein R7 and m are the same as defined herein above; ii) C3-C10 linear, C3-C10 branched linear, C3-C10 cyclic, C3-C10 branched cyclic alkylene, C6-C10 arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties which provide said diamine with a pKa greater than about 8; and iii) mixtures of (i) and (
  • prefe ⁇ ed diamines examples include the following: dimethyl aminopropyl amine, 1,6-hexane diamine, 1,3 propane diamine, 2-methyl 1,5 pentane diamine, 1,3-Pentanediamine (available under the tradename Dytek EP), 1,3- diaminobutane, l,2-bis(2-aminoethoxy)ethane, (available under the tradename Jeffamine EDR 148), Isophorone diamine, l,3-bis(methylamine)-cyclohexane, and mixtures thereof.
  • compositions of the present invention may optionally contain a polymeric suds stabilizer.
  • These polymeric suds stabilizers provide extended suds volume and suds duration without sacrificing the grease cutting ability of the liquid detergent compositions.
  • These polymeric suds stabilizers are preferably selected from: i) homopolymers of (N,N-dialkylamino)alkyl acrylate esters having the formula:
  • each R is independently hydrogen, Cj-Cs alkyl, and mixtures thereof, R 1 is hydrogen, Ci -Cg alkyl, and mixtures thereof, n is from 2 to about 6; and ii) copolymers of (i) and wherein R 1 is hydrogen, C1-C6 alkyl, and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2;
  • the molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, more preferably from about 10,000 to about 750,000, more preferably from about 20,000 to about 500,000, even more preferably from about 35,000 to about 200,000.
  • the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N- dimethylamino)alkyl acrylate ester.
  • a salt either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N- dimethylamino)alkyl acrylate ester.
  • One prefe ⁇ ed polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely
  • the composition will preferably contain at least about 0.01 %, more preferably at least about 0.05%>, even more preferably still, at least about 0.1% by weight of the composition of polymeric suds booster.
  • the cleaning composition will also preferably contain no more than about 15 >, more preferably no more than about 10% ⁇ , even more preferably, no more than about 5%> by weight of the composition of polymeric suds booster.
  • suds stabilizers are the cationic copolymer stabilizers, which contain approximately by weight, more than 50% of units derived from acrylamide, methacrylamide or a mixture thereof, 0.5 to 2% of pendant quaternary nitrogen, and 0.1 to 10% of pendant C.
  • the copolymer contains, approximately by weight, 55 to 95 %> of units derived from acrylamide, methacrylamide or a mixture thereof, 4 to 30%> of hydrophilically functional units having the molecular configuration of units derived from at least one monoethylenically unsaturated, quaternary ammonium group-containing monomer, and 1 to 15%) of units derived from at least one monoethylenically unsaturated, C.sub.8-24 hydrophobic group-containing monomer devoid of quaternary nitrogen. It is more prefe ⁇ ed that the quaternary ammonium group-containing monomer has the formula
  • Ri is H or CH 3
  • R and R 3 are independently C alkyls
  • R 4 is C M alkyl, C -3 hydroxyalkyl, or benzyl
  • R 2 , R 3 and R4 together contain less than 9 carbon atoms
  • Z is a water-solubilizing salt- forming anion
  • M may be — CO— X ⁇ , then X is — O— or --NR 5 —
  • R 5 is H or C 1-4 alkyl and x is 1-6, or M may be phenylene then x is 1; and . that the hydrophobic group-containing monomer has the formula
  • CH 2 C-CO-X-Y y -R 6 Rl
  • Ri is H or CH 3
  • X is -O ⁇ or -NR 7 -
  • Y is -C 2 H 4 O ⁇ or -C 3 H 7 O ⁇
  • y is 0-60
  • R ⁇ is C 8-24 hydrocarbyl
  • Re is C 1- 4 hydrocarbyl and R 7 is H or C 1- 4 hydrocarbyl, at least one of R ⁇ and R 7 being C 8-24 hydrocarbyl.
  • Thickener - The dishwashing detergent compositions herein can also contain from about 0.2% to 5%> of a thickening agent. More preferably, such a thickener will comprise from about 0.5% to 2.5%o of the compositions herein.
  • Thickeners are typically selected from the class of cellulose derivatives. Suitable thickeners include hydroxy ethyl cellulose, hydroxyethyl methyl cellulose, carboxy methyl cellulose, Quatrisoft LM200, and the like.
  • a prefe ⁇ ed thickening agent is hydroxypropyl methylcellulose.
  • the composition may preferably contain at least about 0.1 %, more preferably at least about 0.2%, even more preferably still, at least about 5% by weight of the composition of thickener.
  • the composition will also preferably contain no more than about 5%, more preferably no more than about 3%, even more preferably, no more than about 2.5%) by weight of the composition of thickener.
  • the hydroxypropyl methylcellulose polymer has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt.% aqueous solution at 25°C. (ADTMD2363) of about 50,000 to about 100,000 cps.
  • An especially prefe ⁇ ed hydroxypropyl cellulose polymer is Methocel® J75MS-N wherein a 2.0 wt.%, aqueous solution at 25°C. has a viscosity of about 75,000 cps.
  • Especially prefe ⁇ ed hydroxypropyl cellulose polymers are surface treated such that the hydroxypropyl cellulose polymer will ready disperse at 25°C. into an aqueous solution having a pH of at least about 8.5.
  • the hydroxypropyl methylcellulose polymer When formulated into the dishwashing detergent compositions of the present invention, the hydroxypropyl methylcellulose polymer should impart to the detergent composition a Brookfield viscosity of from about 500 to 3500 cps at 25°C. More preferably, the hydroxypropyl methylcellulose material will impart a viscosity of from about 1000 to 3000 cps at 25°C. For pu ⁇ oses of this invention, viscosity is measured with a Brookfield LVTDV-11 viscometer apparatus using an RV #2 spindle at 12 ⁇ m.
  • the clay thickeners are also suitable for use as thickeners.
  • One suitable clay thickener is Laponite.
  • the Laponite clay when used, is present in the instant composition at a concentration of about 0.25% to about 2.0 wt. %>, more preferably about 0.5 to about 1.75 wt. % is a synthetic colored clay optionally having at least about 5.0 wt. % of tetrapotassium py ⁇ ophosphate peptizer which is Laponite RDS.
  • Laponite RDS which is manufactured by Laponite Inorganics of Great Britain has a particle size of ⁇ 2% greater than 250 microns a bulk density of about 1000 Kg/m.sup.3, and a surface area of about 330 m.sup.3 /g.
  • Laponite RD does not have a peptizer and has a particle size of ⁇ 2%> greater than 250 microns, a surface area of about 370 m.sup.2 /g and a bulk density of about 1000 Kg/m.sup.3.
  • the dishwashing composition may also contain a colloid-foaming, expandable clay which functions both as a thickening agent for the formula and as a suspending agent for the abrasive.
  • expandable clays are those classified geologically as smectites and attapulgites. Suitable smectite clays are the montmorillonite clays which are primarily hydrated aluminosilicates and the hectorites which are primarily hydrated magnesium silicates. It should be understood that the proportion of water of hydration in the smectite clays varies with the manner in which the clay has been processed.
  • the amount of water present is not significant because the expandable characteristics of the hydrated smectite clays are dictated by the silicate lattice structure. Additionally, deficit charges in smectite are compensated by cations such as sodium, calcium, potassium, etc., which are sorbed between the three layer (two tetrahedral and one octahedral) clay mineral sandwiches.
  • the smectite clays used in the liquid compositions are commercially available under various trade names such as Thixogel No. 1 and Gelwhite GP from Georgia Kaolin Company (both montmorillonites) and Veegum Pro and Veegum F from R. T. Vanderbilt (both hectorites).
  • a prefe ⁇ ed clay is Gelwhite GP which is a colloidal montmorillonite clay of a high viscosity sold by Georgia Kaolin company.
  • This clay contains about 6% to 10%, by weight of water and is a mixture of the following oxides: 59%> SIO.sub.2, 21%> Al.sub.3 O.sub.3, 1% Fe.sub.2 O.sub.3, 2.4% CaO, 3.8% MgO, 4.1% Na.sub.2 O and 0.4% K.sub.2 O. 100%) by weight of the clay passes through a 200 mesh screen. It disperses readily in water, but requires maximum swelling in water before use. This swelling of the clay is important to eliminate liquid layering. During this swelling process, the clay/water mix builds substantial viscosity.
  • 350 dynes/cm.sub.2 has been judged to be a prefe ⁇ ed yield point for a clay/water mix of Gelwhite GP because at this point the other physical properties of the final composition, e.g., pourability, dispersibility, suspending ability and liquid layering, are acceptable.
  • layering refers to the amount—in millimeters — of clear liquid visible on the surface of the finished formula after aging at 49. degree. C. for one week and for ten weeks.
  • a clay/water mix having a yield point of 350 dynes/cm. sup.2 is acceptable regardless of Gelwhite GP concentration.
  • Another expandable clay material suitable for use in the liquid compositions is classified geologically as attapulgite, a magnesium rich clay.
  • a typical attapulgite analysis yields 55.02% SiO.sub.2 ; 10.24% Al.sub.2 O.sub.3 ; 3.53% Fe.sub.2 O.sub.3 ; 10.49% MgO; 0.47% K.sub.2 O; 9.73% H.sub.2 O removed at 150.degree. C. and 10.13% H.sub.2 O removed at higher temperatures.
  • Attapulgite clays are commercially available under various trade names such as Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals & Chemicals Co ⁇ oration.
  • Attagel 40 Attagel 40
  • Attagel 50 Attagel 150
  • mixtures of smectite clays and attapulgite clays are suitable, too, to provide combinative properties which are not obtained from either class of clay above.
  • a suspension of clay in water is subjected to high-shear mixing for a sufficient time to substantially fully hydrate the clay before its introduction into the organic portion of the formulation.
  • the desired swelling can be accomplished by high speed shearing of an 8% aqueous clay dispersion for 25 minutes.
  • concentrations of clay as low as 1%> to 1.55% and up to a maximum of 3%>, preferably 1.2% to 2%, by weight are effective to stabilize the inventive abrasive composition without adversely affecting its dispersibility in water.
  • the clay/water mix used in the described composition preferably has a yield point of about 350 dynes/ cm , but satisfactory abrasive compositions can be prepared with aqueousclay dispersions having a yield point as low as 300 dynes/ cm 2 and as high as 450 dynes/cm 2 .
  • the foregoing water-insoluble, low-density, abrasives are suspended in the dishwashing liquid composition and their concentration ranges from 3% > to 15%, preferably from 5% to 15%, by weight.
  • small amounts e.g., 1%> to 25% by weight (based upon the total weight of abrasive in the composition), of crystalline abrasives having a Mohs hardness of 2 to 7 such as silica or calcium carbonate maybe substituted for part of the low density abrasive provided that a substantially stable liquid dishwashing composition results.
  • the instant cleaning compositions may optionally contain from about 0 to about 20 wt. %, more preferably about 0.5 to about 10 wt. % of an abrasive.
  • the abrasive is preferably of selected from the group consisting of amo ⁇ hous hydrated silica, calcite which is a limestone calcium carbonate, and polyethylene powder particles and mixtures thereof.
  • a suitable amo ⁇ hous silica (oral grade) to enhance the scouring ability of the composition is provided by Zeoffin.
  • the mean particle size of Zeoff ⁇ n silica is 8 up to 10 mm. Its apparent density is 0.32 to 0.37 g/ml.
  • Another silica is Tixosil 103 made by Rhone-Poulenc.
  • One polyethylene powder suitable for use in the instant invention has a particle size of about 200 to about 500 microns and a density of about 0.91 to about 0.99 g/liter, more preferably about 0.94 to about 0.96.
  • Another prefe ⁇ ed abrasive is calcite used at a concentration of about 0%> to 20 wt. %>, more preferably 1 wt. %> to 10 wt. % and is manufactured by J. M. Huber Co ⁇ oration of Illinois.
  • Calcite is a limestone consisting primarily of calcium carbonate and 1%> to 5%> of magnesium carbonate which has a mean particle size of 5 microns and oil abso ⁇ tion (rubout) of about 10 and a hardness of about 3.0 Mohs.
  • Solvents A variety of water-miscible liquids such as lower alkanols, diols, other polyols, ethers, amines, and the like may be used Particularly prefe ⁇ ed are the C1-C4 alkanols. Such solvents can be present in the compositions herein to the extent of from about 1% to 8%.
  • the composition will preferably contain at least about 0.01%, more preferably at least about 0.5%, even more preferably still, at least about 1%> by weight of the composition of solvent.
  • the composition will also preferably contain no more than about 20%), more preferably no more than about 10%, even more preferably, no more than about 8% by weight of the composition of solvent.
  • solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
  • Solvents are broadly defined as compounds that are liquid at temperatures of 20°C-25°C and which are not considered to be surfactants. One of the distinguishing features is that solvents tend to exist as discrete entities rather than as broad mixtures of compounds. Examples of suitable solvents for the present invention include, methanol, ethanol, propanol, isopropanol, 2-methyl py ⁇ olidinone, benzyl alcohol and mo ⁇ holine n-oxide. Prefe ⁇ ed among these solvents are methanol and isopropanol.
  • Suitable solvents for use herein include ethers and di ethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms.
  • suitable solvents are glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
  • Suitable glycols which can be used herein are according to the formula HO- CR1R2-OH wherein Rl and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic.
  • Suitable glycols to be used herein are dodecaneglycol and/or propanediol.
  • polypropylene glycols such as those with a molecular weigh in the range of about 100 to 1000.
  • One suitable polypropylene glycol ha a molecular weight of about 2700.
  • Suitable alkoxylated glycols which can be used herein are according to the formula R-(A)n-Rl-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein Rl is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
  • Suitable alkoxylated aromatic alcohols which can be used herein are according to the formula R (A) n -OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
  • Suitable aromatic alcohols which can be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
  • a suitable aromatic alcohol to be used herein is benzyl alcohol.
  • Suitable aliphatic branched alcohols which can be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
  • Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
  • Suitable alkoxylated aliphatic branched alcohols which can be used herein are according to the formula R (A) n -OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.
  • Suitable alkoxylated linear C1-C5 alcohols which can be used herein are according to the formula R (A) n -OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
  • Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow chemical.
  • Suitable linear C1-C5 alcohols which can be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
  • Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
  • Suitable solvents include, but are not limited to, butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly prefe ⁇ ed solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • BDGE butyl diglycol ether
  • ter amilic alcohol ter amilic alcohol
  • Particularly prefe ⁇ ed solvents which can be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
  • Suitable solvents for use herein include propylene glycol derivatives such as n-butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a prefe ⁇ ed water-soluble carbitol is 2-(2- butoxyethoxy)ethanol also known as butyl carbitol.
  • Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being prefe ⁇ ed.
  • Other suitable solvents include benzyl alcohol, and diols such as 2- ethyl-1, 3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol and mixtures thereof.
  • Some prefe ⁇ ed solvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL ® and mixtures thereof.
  • the solvents can also be selected from the group of compounds comprising ether derivatives of mono-, di- and tri-ethylene glycol, propylene glycol, butylene glycol ethers, and mixtures thereof.
  • the molecular weights of these solvents are preferably less than 350, more preferably between 100 and 300, even more preferably between 115 and 250.
  • Examples of prefe ⁇ ed solvents include, for example, mono-ethylene glycol n-hexyl ether, mono-propylene glycol n-butyl ether, and tri-propylene glycol methyl ether.
  • Ethylene glycol and propylene glycol ethers are commercially available from the Dow Chemical Company under the tradename "Dowanol” and from the Arco Chemical Company under the tradename “Arcosolv”.
  • Other preferred solvents including mono- and di-ethylene glycol n-hexyl ether are available from the Union Carbide company.
  • Solubilizing agent - The instant compositions may optionally contain about 0 wt. % > to about 12 wt. %>, more preferably about 1 wt. % to about 10 wt.
  • solubilizing agent which can be a hydrotrope such as sodium xylene sulfonate, or sodium cumene sulfonate, a C -3 mono or dihydroxy alkanols such as ethanol, isopropanol and propylene glycol and mixtures thereof.
  • the solubilizing agents are included in order to control low temperature cloud clear properties.
  • Urea can be optionally employed in the instant composition as a supplemental solubilizing agent at a concentration of 0 to about 10 wt. %>, more preferably about 0.5 wt. %> to about 8 wt. %>.
  • solubilizing agents are glycerol, water-soluble polyethylene glycols having a molecular weight of 300 to 600, polypropylene glycol of the formula HO(CH 3 CHCH O) n H wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and mono Ci -C 6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X) confrontOH and R ⁇ (X) n OH wherein R is Ci -C 6 alkyl group, Ri is C 2 - C 4 acyl group, X is (OCH 2 CH 2 ) or (OCH 2 (CH 3 )CH) and n is a number from 1 to 4.
  • glycerol water-soluble polyethylene glycols having a molecular weight of 300 to 600
  • Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400.
  • Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol mono
  • compositions according to the present invention may optionally comprise one or more soil release agents.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and , thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • soil release agents will generally comprise from about 0.01%> to about 10% preferably from about 0.1 %> to about 5%, more preferably from about 0.2%> to about 3%> by weight, of the composition.
  • compositions of the present invention can also optionally contain polymeric grease release agents.
  • Sutable polymer grese release agents include those of the formula:
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0%> by weight of the water- soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%.
  • a prefe ⁇ ed soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of prefe ⁇ ed clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.
  • Another type of prefe ⁇ ed antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1 % to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release, peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a prefe ⁇ ed component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol te ⁇ olymers.
  • Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal- antiredeposition agent.
  • Typical molecular weight ranges for these pu ⁇ oses range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • polystyrene resin examples include various te ⁇ olymers and hydrophobically modified copolymers, including those marketed by Rohm & Haas, BASF Co ⁇ ., Nippon Shokubai and others for all manner of water-treatment, textile treatment, or detergent applications.
  • compositions herein may also optionally contain one or chelating agents, particularly chelating agents for adventitious transition metals.
  • chelating agents particularly chelating agents for adventitious transition metals.
  • Those commonly found in wash water include iron and/or manganese in water-soluble, colloidal or particulate form, and may be associated as oxides or hydroxides, or found in association with soils such as humic substances.
  • Prefe ⁇ ed chelants are those which effectively control such transition metals, especially including controlling deposition of such transition-metals or their compounds on fabrics and/or controlling undesired redox reactions in the wash medium and/or at fabric or hard surface interfaces.
  • Such chelating agents include those having low molecular weights as well as polymeric types, typically having at least one, preferably two or more donor heteroatoms such as O or N, capable of co-ordination to a transition-metal.
  • Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetrace-tates, N-hydroxyethylethylenediaminetriacetates, nitrilo-tri- acetates, ethylenediamine tetrapro-prionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Prefe ⁇ ed, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Prefe ⁇ ed compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder.
  • MGDA water-soluble methyl glycine diacetic acid
  • so called "weak” builders such as citrate can also be used as chelating agents.
  • chelating agents will generally comprise from about 0.001 %> to about 15% by weight of the detergent compositions herein. More preferably, if utilized, chelating agents will comprise from about 0.01%> to about 3.0%> by weight of such compositions.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention when required by the intended use, especially washing of laundry in washing appliances.
  • Other compositions, such as those designed for hand-washing, may desirably be high-sudsing and may omit such ingredients Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • compositions herein will generally comprise from 0%, to about 10%, of suds suppressor.
  • monocarboxyhc fatty acids, and salts thereof will be present typically in amounts up to about 5%>, preferably 0.5%> - 3%> by weight, of the detergent composition, although higher amounts may be used.
  • weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any suds suppressor adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1 %> to about 2%>, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01%> to about 5.0%>, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3%> by weight of the finished compositions.
  • Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance.
  • Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., inco ⁇ orated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units.
  • the side-chains are of the formula -(CH2CH2O) m (CH2) n CH3 wherein m is 2-3 and n is 6-12.
  • the side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure.
  • the molecular weight can vary, but is typically in the range of about 2000 to about 50,000.
  • Such alkoxylated polycarboxylates can comprise from about 0.05%> to about 10%, by weight, of the compositions herein.
  • Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01%> to about 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from about 0.0001% to about 90%) of a finished perfume composition.
  • Non-limiting examples of perfume ingredients useful herein include: 7-acetyl- 1, 2,3,4,5,6,7, 8-octahydro-l,l,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-trimethyl- 2,5,9-cyclododecatrien-l-yl ketone; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; 4-acetyl-6- tert-butyl- 1,1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l, 1,2,3,3, 5-hexamethyl indane; 5-acetyl-3-isopropyl- 1,1,2,6-tetramethyl indane; 1-dodecan
  • perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases.
  • These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert- butylphenyl)-propionaldehyde; 7-acetyl-l, 2,3,4,5,6,7, 8-octahydro-l,l,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta- naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8- hexahydro-4,6,6,6,
  • perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
  • Still other perfume chemicals include phenyl ethyl alcohol, te ⁇ ineol, linalool, linalyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
  • Carriers such as diethylphthalate can be used in the finished perfume compositions.
  • compositions can employ an essential oil or a water insoluble organic compound such as a water insoluble hydrocarbon having 6 to 18 carbon such as a paraffin or isoparaffin such as isoparH, isodecane, alpha-pinene, beta-pinene, decanol and te ⁇ ineol.
  • a water insoluble organic compound such as a water insoluble hydrocarbon having 6 to 18 carbon such as a paraffin or isoparaffin such as isoparH, isodecane, alpha-pinene, beta-pinene, decanol and te ⁇ ineol.
  • Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69. degree. C.
  • composition pH - Dishwashing compositions of the invention will be subjected to acidic stresses created by food soils when put to use, i.e., diluted and applied to soiled dishes. If a composition with a pH greater than 7 is to be more effective, it may optionally contain i l l
  • a buffering agent capable of providing a generally more alkaline pH in the composition and in dilute solutions, i.e., about 0.1%, to 0.4% by weight aqueous solution, of the composition.
  • the pKa value of this buffering agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above).
  • the pKa of the buffering agent should be from about 7 to about 10. Under these conditions the buffering agent most effectively controls the pH while using the least amount thereof.
  • compositions of the present invention has a pH (as measured as 10% aqueous solution) from about 2.0 to about 12.5, more preferably from about to about , even more preferably from about to about .
  • the buffering agent may be an active detergent in its own right, or it may be a low molecular weight, organic or inorganic material that is used in this composition solely for maintaining an alkaline pH.
  • Prefe ⁇ ed buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine.
  • nitrogen-containing buffering agents are Tri(hydroxymethyl)amino methane (HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-l,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-l,3-propanol, disodium glutamate, N-methyl diethanolamide, 1,3- diamino-propanol N,N'-tetra-methyl- 1 ,3-diamino-2-propanol, N,N-bis(2- hydroxyethyl)glycine (bicine) and N-tris (hydroxymethyl)methyl glycine (tricine).
  • Tri(hydroxymethyl)amino methane (HOCH2)3CNH3 TriS
  • 2-amino-2-ethyl-l,3-propanediol 2-amino-2-methyl-propanol
  • 2-amino-2-methyl-l,3-propanol dis
  • inorganic buffers/alkalinity sources include the alkali metal carbonates and alkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • alkali metal carbonates and alkali metal phosphates e.g., sodium carbonate, sodium polyphosphate.
  • McCutcheon's EMULSIFIERS AND DETERGENTS North American Edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971 both of which are inco ⁇ orated herein by reference.
  • the composition will preferably contain at least about 0.1%, more preferably at least about 1%, even more preferably still, at least about 2%, by weight of the composition of buffering agent.
  • the composition will also preferably contain no more than about 15%, more preferably no more than about 10%, even more preferably, no more than about 8% by weight of the composition of buffering agent.
  • Hydrotropes -
  • the aqueous liquid carrier may comprise one or more materials which are hydrotropes.
  • Hydrotropes suitable for use in the compositions herein include the C1 -C3 alkyl aryl sulfonates, C6-C12 alkanols, C ⁇ -Cg carboxylic sulfates and sulfonates, urea, C j -Cg hydrocarboxylates, C1-C4 carboxylates, C2-C4 organic diacids and mixtures of these hydrotrope materials.
  • the liquid detergent composition of the present invention preferably comprises from about 0.5%> to 8%>, by weight of the liquid detergent composition of a hydrotrope selected from alkali metal and calcium xylene and toluene sulfonates.
  • Suitable C1-C3 alkyl aryl sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates; sodium, potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium and ammonium cumene sulfonates; and sodium, potassium, calcium and ammonium substituted or unsubstituted naphthalene sulfonates and mixtures thereof.
  • Suitable C1 -C carboxylic sulfate or sulfonate salts are any water soluble salts or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulfate or sulfonate and have at least one carboxylic group.
  • the substituted organic compound may be cyclic, acylic or aromatic, i.e. benzene derivatives.
  • Prefe ⁇ ed alkyl compounds have from 1 to 4 carbon atoms substituted with sulfate or sulfonate and have from 1 to 2 carboxylic groups.
  • hydrotrope examples include sulfosuccinate salts, sulfophthalic salts, sulfoacetic salts, m- sulfobenzoic acid salts and diester sulfosuccinates, preferably the sodium or potassium salts as disclosed in U.S. 3,915,903.
  • Suitable C1-C4 hydrocarboxylates and C1 -C4 carboxylates for use herein include acetates and propionates and citrates.
  • Suitable C2-C4 diacids for use herein include succinic, glutaric and adipic acids.
  • hydrotrope examples include C6-C12 alkanols and urea.
  • Prefe ⁇ ed hydrotropes for use herein are sodium, potassium, calcium and ammonium cumene sulfonate; sodium, potassium, calcium and ammonium xylene sulfonate; sodium, potassium, calcium and ammonium toluene sulfonate and mixtures thereof. Most prefe ⁇ ed are sodium cumene sulfonate and calcium xylene sulfonate and mixtures thereof. These prefe ⁇ ed hydrotrope materials can be present in the composition to the extent of from about 0.5%> to 8%> by weight.
  • the composition will preferably contain at least about 0.1 %>, more preferably at least about 0.2%>, even more preferably still, at least about 0.5%> by weight of the composition of hydrotrope.
  • the composition will also preferably contain no more than about 15%,, more preferably no more than about 10%,, even more preferably, no more than about 8%> by weight of the composition of hydrotrope.
  • the detergent compositions may further preferably comprise one or more detersive adjuncts selected from the following: soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, color stabilizers, dyes, electrolytes( such as NaCl etc), antifungal or mildew control agents, insect repellents, acaricidal agents hydrotropes, processing aids, suds boosters, brighteners, anti- co ⁇ osive aids and stabilizers antioxidants.
  • soil release polymers polymeric dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, color stabilizers, dyes, electrolytes( such as NaCl etc), antifungal or mildew control agents, insect repellents, acaricidal agents hydrotropes, processing aids, suds boosters, brighteners, anti- co ⁇ osive aids and stabilizers antioxidants.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the CI Q-C ⁇ alkanolamides can be inco ⁇ orated into the compositions, typically at 1%>-10%> levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • An antioxidant can be optionally added to the detergent compositions of the present invention. They can be any conventional antioxidant used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine(MEA), diethanolamine, triethanolamine, etc. It is prefe ⁇ ed that the antioxidant, when present, be present in the composition from about 0.001% to about 5% by weight.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • MEA monoethanolamine
  • MEA diethanolamine
  • triethanolamine triethanolamine
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of Ci3_i5 ethoxylated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500- 12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500- 12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • compositions herein can be in any of the conventional forms for hand dishwashing compositions, such as, paste, liquid, granule, powder, gel, liqui-gel, microemulsion liquid crystal and mixtures thereof. Highly prefe ⁇ ed embodiments are in liquid or gel form.
  • the liquid compositions can be either aqueous or nonaqueous. When the composition is a aqueous liquid the composition will preferably further contain an aqueous liquid carrier in which the other essential and optional compositions components are dissolved, dispersed or suspended.
  • composition When the composition is an aqueous liquid the composition will preferably contain at least about 5%>, more preferably at least about 10%,, even more preferably still, at least about 30%, by weight of the composition of aqueous liquid carrier.
  • the composition will also preferably contain no more than about 95%,, more preferably no more than about 60%,, even more preferably, no more than about 50%, by weight of the composition of aqueous liquid carrier.
  • the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature and which may also serve some other function besides that of a simple filler.
  • Such materials can include, for example, hydrotropes and solvents.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are prefe ⁇ ed for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3- propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3- propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • An example of the procedure for making granules of the detergent compositions herein is as follows: - the modified aklylbenzenesulfonate, citric acid, sodium silicate, sodium sulfate perfume, diamine and water are added to, heated and mixed via a crutcher. The resulting slurry is spray dried into a granular form.
  • liquid detergent compositions which comprise a non-aqueous carrier medium can be prepared according to the disclosures of U.S. Patents 4,753,570; 4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A- 2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S.
  • compositions can contain various particulate detersive ingredients stably suspended therein.
  • non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
  • compositions of this invention can be used to form aqueous washing solutions for use hand dishwashing.
  • an effective amount of such compositions is added to water to form such aqueous cleaning or soaking solutions.
  • the aqueous solution so formed is then contacted with the dishware, tableware, and cooking utensils.
  • An effective amount of the detergent compositions herein added to water to form aqueous cleaning solutions can comprise amounts sufficient to form from about 500 to 20,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous cleaning liquor.
  • R2O(CnH2nO)t(glycosyl)x of given chainlength Cxy where R2 is a Cio-is alkyl; n is 2 or 3, t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • amylase is selected from: Fungamyl®; Duramyl®; BAN®; and ⁇ amylase enzymes described in WO95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • DEA diethanolamine Diamine Alkyl diamine e.g., 1,3 propanediamine, Dytek EP,
  • Dytek A (Dupont) or selected from: dimethyl aminopropyl amine; 1,6-hexane diamine; 1,3 propane diamine; 2-methyl 1,5 pentane diamine; 1,3- pentanediamine; 1-methyl-diaminopropane; 1,3 cyclohexane diamine; 1,2 cyclohexane diamine; 1,3- bis(methylamine)-cyclohexane
  • EtOH Ethanol Hydrotrope selected from sodium, potassium, Magnesium,
  • Lipase Lipolytic enzyme lOOkLU/g, NOVO, Lipolase®.
  • the lipase is selected from: Amano-P;
  • MA/AA Copolymer 1 4 maleic/acrylic acid, Na salt, avg. mw.
  • MBAyS Mid-chain branched primary alkyl sulfate, Na salt
  • Magnesium Salt Magnesium chloride, Magnesium sulfate, magnesium hydroxide, and mixtures thereof
  • the protease is selected from: Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®-
  • Silicate Sodium Silicate, amo ⁇ hous SiO2:Na2O; 2.0 ratio
  • ingredients can include perfumes, dyes, pH trims etc.
  • the following example is illustrative of the present invention, but is not meant to limit or otherwise define its scope. All parts, percentages and ratios used are expressed as percent weight unless otherwise noted.
  • Viscosity (cps 150 330 650 330
  • Viscosity (cps 330 330
  • a shape selective zeolite catalyst acidic beta zeolite catalyst
  • ZeocatTM PB/H are added to a 2 gallon stainless steel, sti ⁇ ed autoclave. Residual olefin and catalyst in the container are washed into the autoclave with 300 mL of n-hexane and the autoclave is sealed. From outside the autoclave cell, 2000 g of benzene (contained in a isolated vessel and added by way of an isolated pumping system inside the isolated autoclave cell) is added to the autoclave. The autoclave is purged twice with 250 psig
  • the mixture is sti ⁇ ed and heated to about 200°C for about 4-5 hours.
  • the autoclave is cooled to about 20°C overnight.
  • the valve is opened leading from the autoclave to the benzene condenser and collection tank.
  • the autoclave is heated to about 120°C with continuous collection of benzene. No more benzene is collected by the time the reactor reaches 120°C.
  • the reactor is then cooled to 40°C and 750 g of n-hexane is pumped into the autoclave with mixing.
  • the autoclave is then drained to remove the reaction mixture.
  • the reaction mixture is filtered to remove catalyst and the n-hexane is removed under vacuum.
  • a modified alkylbenzene mixture with a 2/3-Phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02 is collected from 76°C - 130°C (167 g).
  • EXAMPLE 28 Modified Alkylbenzenesulfonic Acid Mixture according to the invention (Branched and Nonbranched Alkylbenzenesulfonic Acid Mixture) with a 2/3-Phenyl Index of about 200 and a 2-Methyl-2-Phenyl Index of about 0.02
  • the modified alkylbenzene mixture of example 27 is sulfonated with a molar equivalent of chlorosulfonic acid using methylene chloride as solvent. The methylene chloride is removed to give 210 g of a modified alkylbenzenesulfonic acid mixture with a 2/3- Phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02.
  • EXAMPLE 29 Modified Alkylbenzenesulfonate, Sodium Salt Mixture
  • Branched and Nonbranched Alkylbenzenesulfonate, Sodium Salt Mixture with a 2/3-Phenyl Index of about 200 and a 2-Methyl-2-Phenyl Index of about 0.02
  • the modified alkylbenzenesulfonic acid of example 28 is neutralized with a molar equivalent of sodium methoxide in methanol and the methanol is evaporated to give 225 g of a modified alkylbenzenesulfonate, sodium salt mixture with a 2/3-Phenyl index of about 200 and a 2-methyl-2-phenyl index of about 0.02.

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  • Engineering & Computer Science (AREA)
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Abstract

Cette invention se rapporte à des mélanges de tensioactifs, à des produits détergents et à des produits de nettoyage améliorés contenant des types particuliers de tensioactifs à l'alkylbenzènesulfonate.
PCT/US1999/029838 1999-01-20 1999-12-15 Compositions de lavage de la vaisselle comprenant un alkylbenzene modifie WO2000043474A2 (fr)

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JP2000594883A JP2002535439A (ja) 1999-01-20 1999-12-15 改質アルキルベンゼンを含む皿洗い用組成物
EP99965276A EP1144568A3 (fr) 1999-01-20 1999-12-15 Compositions de lavage de la vaisselle comprenant un alkylbenzene modifie
BR9916936-3A BR9916936A (pt) 1999-01-20 1999-12-15 Composições para lavagem de pratos compreendendo alquil benzenos modificados

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CN102008419A (zh) * 2010-12-10 2011-04-13 中国人民武装警察部队医学院 清理护肤液
JP2013082847A (ja) * 2011-10-12 2013-05-09 Kao Corp 手洗い用食器洗浄剤組成物
JP2014037503A (ja) * 2012-08-20 2014-02-27 Kao Corp 繊維製品用液体洗浄剤組成物
JP2015218226A (ja) * 2014-05-15 2015-12-07 ライオン株式会社 液体洗浄剤及びその製造方法
US10005986B2 (en) 2007-02-15 2018-06-26 Ecolab Usa Inc. Fast dissolving solid detergent
EP2295530B2 (fr) † 2009-09-14 2019-04-17 The Procter & Gamble Company Composition de détergent
US11535815B2 (en) 2016-10-31 2022-12-27 Sabic Global Technologies B.V. Glycerin ethoxylate as an active ingredient in removing make-up stain
EP2264138B2 (fr) † 2009-06-19 2023-03-08 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
US11659838B2 (en) 2021-04-01 2023-05-30 Sterilex, Llc Quat-free powdered disinfectant/sanitizer

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AR061906A1 (es) * 2006-07-18 2008-10-01 Novapharm Res Australia Limpiador de baja espuma
ES2412684T3 (es) * 2009-06-19 2013-07-12 The Procter & Gamble Company Composición detergente de lavado de vajillas a mano líquida
EP2557145A1 (fr) * 2011-06-28 2013-02-13 SASOL Germany GmbH Compositions d'agents tensioactifs
CN103060114A (zh) * 2013-01-07 2013-04-24 洛娃科技实业集团有限公司 具有速干功效的洗洁精
ES2704092T3 (es) * 2014-04-30 2019-03-14 Procter & Gamble Composición limpiadora
AU2016321761B2 (en) * 2015-09-15 2019-03-07 Unilever Global Ip Limited Aqueous hard surface cleaning composition

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WO1999005244A1 (fr) * 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999007656A2 (fr) * 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
WO2000012451A1 (fr) * 1998-09-02 2000-03-09 The Procter & Gamble Company Procedes ameliores permettant de produire des tensioactifs par separation par adsorption, et produits y relatifs

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EP0615968A1 (fr) * 1991-12-23 1994-09-21 Uop Procédé d'alkylation de benzène en utilisant une silice-alumine fluorée et une monooléfine linéaire en C6 à C20
WO1999005244A1 (fr) * 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999007656A2 (fr) * 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
WO2000012451A1 (fr) * 1998-09-02 2000-03-09 The Procter & Gamble Company Procedes ameliores permettant de produire des tensioactifs par separation par adsorption, et produits y relatifs

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10005986B2 (en) 2007-02-15 2018-06-26 Ecolab Usa Inc. Fast dissolving solid detergent
US10577565B2 (en) 2007-02-15 2020-03-03 Ecolab Usa Inc. Fast dissolving solid detergent
US11261406B2 (en) 2007-02-15 2022-03-01 Ecolab Usa Inc. Fast dissolving solid detergent
EP2264138B2 (fr) † 2009-06-19 2023-03-08 The Procter & Gamble Company Composition de détergent liquide pour lavage de la vaisselle à la main
EP2295530B2 (fr) † 2009-09-14 2019-04-17 The Procter & Gamble Company Composition de détergent
CN102008419A (zh) * 2010-12-10 2011-04-13 中国人民武装警察部队医学院 清理护肤液
JP2013082847A (ja) * 2011-10-12 2013-05-09 Kao Corp 手洗い用食器洗浄剤組成物
JP2014037503A (ja) * 2012-08-20 2014-02-27 Kao Corp 繊維製品用液体洗浄剤組成物
JP2015218226A (ja) * 2014-05-15 2015-12-07 ライオン株式会社 液体洗浄剤及びその製造方法
US11535815B2 (en) 2016-10-31 2022-12-27 Sabic Global Technologies B.V. Glycerin ethoxylate as an active ingredient in removing make-up stain
US11659838B2 (en) 2021-04-01 2023-05-30 Sterilex, Llc Quat-free powdered disinfectant/sanitizer

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EP1144568A3 (fr) 2002-09-11
BR9916936A (pt) 2002-03-19
CN1361814A (zh) 2002-07-31
AR016745A1 (es) 2001-07-25

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